FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
AND
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
TITLE OF THE INVENTION
"Stereospecific Synthesis of Nitro Olefin"
APPLICANT
Indian Institute of Technology, Bombay of Powai, Mumbai 400076, Maharastra, India; Indian
INVENTORS
Prof. Debabrata Maiti, Soham Maity, Srimanta Manna and Sujoy Rana
all Indian Nationals of Indian Institute of Technology, Bombay,
Department of Chemistry, Powai, Mumbai-400076,
Maharastra, India
The following specification particularly describes the invention and the manner in which it is to be performed

FIELD OF THE INVENTION:
The present invention relates to a method for nitroolefin synthesis using silver nitrite or ferric nitrate or tert-butyl nitrite as the nitrating agent in combination with TEMPO. The process of the present invention is a thermally driven one, is practical, economical, convenient, utilizing mild reaction conditions and tolerating a wide array of functional groups. Wide ranges of olefins were surveyed and it was found that nitration was successfully occurring on aromatic, aliphatic and heteroaromatic double bonds with equal ease.
BACKGROUND OF THE INVENTION
Synthesis of nitro olefins is of great significance as they are widely used as synthons in various carbon-carbon bond-forming reactions like Michael reaction1'4 and Diels-Alder reaction.5"14 In Diels-Alder reactions, nitro olefin moieties usually play the role of a dienophile though they are used as dienes also. The nitro group can be converted further to different functionalities leading to corresponding oximes,'5 hydroxylamines, nitroalkanes,16 aliphatic amines and nitroso compounds.7'8 Upon reduction, nitroalkanes and aliphatic amines can be generated depending on the nature of the reducing agent deployed. Moreover, nitroolefins are used as building blocks in synthesis of different complex molecules, which are relevant in biological and pharmaceutical aspects.6
Conventionally nitroolefins are synthesized by Henry reaction,7,17,18 the base catalyzed condensation of an aldehyde with a nitroalkane leading to nitroaldol product, which is then converted to nitroolefin by dehydration. Certainly the simplest and convenient synthesis would be replacement of a hydrogen atom of the olefin with a nitro group. Following this approach, chemists have tried to synthesize nitroolefins and various methods have been developed19-27 by using different nitrating agents such as HN03/H2SO4, NaNO2/HgCl2, AgNO2/I2, NaN02/Cu(lI)-I2, etc. Also, several gaseous reagents like NO, N02/O3 have been used as the nitrating agents. However, all these methods are limited by either employing harsh or not so easy to handle reaction condition, or suffer from poor substrate scope that lacks both in functional group tolerance and variety of substrates.19-27 To the best of our knowledge, no heterocyclic olefin or olefin of natural product origin have been nitrated following these methods.

Previous reports invariably form a mixture of E/Z products and no stereospecific synthesis of nitroolefins has been reported till date.19-27 Therefore an efficient, general, practical, regio- and stereospecific method for nitroolefin synthesis remains a challenging scientific problem.
Thus, there also remains a need for an efficient process for nitroolefin synthesis that affords high yields of the respective nitroolefin products. It would therefore be highly desirable to provide a process, which facilitates an efficient nitroolefin synthesis that circumvents the aforesaid drawbacks of the prior art processes.
Accordingly, the inventors of the present invention have endeavored to provide a rapid and robust method for synthesis of nitroolefins through a user-friendly, thermally driven nitration strategy. It has been found that, if an olefin is reacted under this condition, the nitro radical reacts with the double bond thereby generating a carbon centered radical which further oxidizes to give the corresponding nitroolefin. This carbon center radical is formed at the more substituted or benzylic position and hence regioselectivity of the reaction is determined by radical stability
28-31
alone. An exogenous radical (such as TEMPO) intercepts the carbon centered radical and anti-elimination results in nitroolefin formation in regiospecific fashion.
Accordingly, the present inventors report a convenient method of nitroolefin synthesis by using an appropriate nitrating agent and widely used oxylradical, TEMPO. The new nitration strategy as described in the instant invention exhibits a wide array of substrate scope ranging from heterocyclic aromatic olefins to terminal and non-terminal aliphatic alkenes. Also, the method afforded by the present invention requires a simple work-up procedure and is therefore economical, efficient and easily scalable.
OBJECT OF THE INVENTION:
In accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention provides for a region- and stereospecific method of synthesizing nitroolefins under (i) mild reaction conditions (ii) rendering a broad substrate scope and

tolerance towards a wide range of functional groups (iii) the process being efficient, economic and scalable.
A further object of the present invention is to provide for a method of synthesizing nitroolefins employing a suitable nitrating agent such as silver nitrite or ferric nitrate or tert-butyl nitrite and an oxylradical, TEMPO under conditions effective to yield the corresponding nitroolefin in good yields.
Yet another object of the present invention is to provide the process of nitration, which is preferably carried out in the presence of dichloroethane (DCE) as a solvent at about 70 °C. The process of nitration as described in the present invention successfully occurs on aromatic, aliphatic and heteroaromatic double bonds with equal ease.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration only, because various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF DRAWINGS
The foregoing summary, as well as the following detailed description of preferred embodiments of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. In the drawings:
Figure 1: ORTEP diagram of crystal structure (CCDC 905717) of plausible intermediate
Figure 2: Pictorial description of reaction tube for nitration of olefin: Fisherbrand Disposable Borosilicate Glass Tubes (16* 125mm) with Threaded End (Fisher Scientific Order No. 1495935A) [left]; Kimble Black Phenolic Screw Thread Closures with Open Tops (Fisher Scientific Order No. 033407E) [middle]; Thermo Scientific National PTFE/Silicone Septa for

Sample Screw Thread Caps (Fisher Scientific Order No. 03394A) [right]. Reactions with ferric nitrate were performed in a larger glass tube (20*150 MM) of the same brand.
DETAILED DESCRIPTION OF THE INVENTION
In describing and claiming the invention, the following terminology will be used in accordance with the definitions set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. As used herein, each of the following terms has the meaning associated with it in this section. Specific and preferred values listed below for individual process parameters, substituents, and ranges are for illustration only; they do not exclude other defined values or other values falling within the preferred defined ranges.
As used herein, the singular forms "a," "an," and "the" include plural reference unless the context clearly dictates otherwise.
The terms "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
When the term "about" is used in describing a value or an endpoint of a range, the disclosure should be understood to include both the specific value or end-point referred to.
As used herein the terms "comprises", "comprising", "includes", "including", "containing", "characterized by", "having" or any other variation thereof, are intended to cover a nonexclusive inclusion.
The term olefin, also called alkene, refers to any unsaturated hydrocarbon containing one or more pairs of carbon atoms linked by a double bond. The olefins are classified in either or both of the following ways: (1) as cyclic or acyclic (aliphatic) olefins, in which the double bond is

located between carbon atoms forming part of a cyclic (closed-ring) or of an open-chain grouping, respectively, and (2) as monoolefins, diolefins, triolefins, etc., in which the number of double bonds per molecule is, respectively, one, two, three, or some other number.
A nitroolefin refers to a nitro derivative of an olefin.
The present invention pertains to a process for nitration of olefins comprising contacting the olefin with a solvent such as dichloroethane in the presence of a nitrating agent and TEMPO that promote the nitration of the olefin to yield a nitroolefin product in good yield.
Without being bound to any theory, it has been found that if an olefin is reacted under the nitration strategy, the nitro radical reacts with the double bond thereby generating a carbon centered radical which further oxidizes to give the corresponding nitroolefin (Scheme 1). This carbon center radical is formed at the more substituted or benzylic position and hence regioselectivity of the reaction is determined by radical stability alone. An exogenous radical (such as TEMPO) intercepts the carbon centered radical and anti-elimination results in nitroolefin formation in regiospecific fashion.

More particularly, the present invention relates to a method of nitroolefin synthesis by employing silver nitrite and ferric nitrate as the nitrating agent and an oxylradical, TEMPO under conditions represented in Scheme 2 depicted below.
According to one embodiment, a range of nitroolefins were synthesized, characterized and their thermal properties analysed. The nitration strategy presented below exhibits a wide array of

substrate scope ranging from heterocyclic, aromatic olefins to terminal and non-terminal aliphatic alkenes.
SCHEME - 2

Preferred nitrating agents are selected from the group comprising AgN02, Fe(N03)3.9H20, Bi(N03)3.5H2O, Co(N03)2.6H2O,Na3Co(N02)6, Pr(N03)2,6H20, Cd(N03)2 and tert-butyl nitrite. The most preferred nitration agent in context of the present invention is AgN02 or Fe(N03)3.9H2O or tert-butyl nitrite.
The process of the present invention is prepared preferably with a solvent selected from the group comprising dichloroethane (DCE), benzene. Dichloromethane (DCM), DMSO, acetonitrile, CHC13, dioxane and the like. Polar and non polar solvents provide comparative results. In order to realize the advantageous attributes of the present invention, it is preferred to employ dichloroethane (PCE) as a suitable solvent.
According to a significant aspect of the invention, a suitable oxylradical such as TEMPO is employed for the nitration reaction. The employment of TEMPO as an additive was found to be very effective as it lead to complete conversion of starting material and P-nitro styrene was obtained in 95% isolated yield. Interestingly, addition of TEMPO resulted in preferred increase in yield of the desired product with bismuth (III)and iron (III) and tert-butyl nitrates/nitrite.
According to a preferred embodiment of the present invention, a gram scale reaction resulted in 88% isolated yield of the desired product indicating that this protocol may be applicable in industrial purpose (Scheme 3)
SCHEME 3 - Gram scale reaction with styrene


SCHEME 4 - Scope of Styrene derivativesa

Isolated yield of the E isomer as determined by the 'H NMR analysis. Olefin (0.5 mmol), AgN02 (1.5 mmol), TEMPO (0.2 mmol), 150 mg MS, 70°C, DCE (2 mL). b0.25 mmol substrate, 1.2 mmol AgN02 and 0.15 mmol TEMPO; Cyields correspond to E isomer only, E/Z ratio determined by GC-MS analysis of the reaction mixture. d0.25 mmol substrate, 0.75 mmol AgNO2 and 0.1 mmol TEMPO, 80 mg molecular sieves (4 A), 1 mL DCE.
The substrate scope of the metal mediated synthesis of nitro olefins was evaluated. The reaction worked quite well with different substituted styrene derivatives (Scheme 4, 4a-4r, 66-97% yield). Both electron donating (4a, 4b and 4j) as well as electron withdrawing (4c-4h) group containing styrenes were nitrated in excellent yield. A wide array of functional group ranging from strongly electron donating -OMe, -NH2, -NHCOR to strongly electron withdrawing -CHO, -NO2, -CO2Me, -CN were well tolerated. Even different halogen substituted (-F, -CI, -Br) styrenes were

nitrated with equal ease (4e, 4f and 4k 92-97% yield). These functional groups can be converted selectively without affecting the nitro group thereby generating further nitroolefin derivatives. Substituents on the a- (4m and 4o) and (3- position (4n) of the double bond of styrene had little or no effect on the yield. Also both cis- and trans-stilbenes resulted in E nitro product only indicating the stereospecific nature of the reaction as predicted. Sterically demanding substrates like 2,4,6-trimethyl styrene (4q) was also nitrated in an excellent 93% yield. Even, styrene derivative with captodative functional groups (4p) was also nitrated in considerably high yield. 1,2-divinylbenzene was selectively mono-nitrated in 70% yield under the usual reaction condition without a trace of di-nitration (4r).
The process of the present invention worked quite well with aliphatic alkenes also. Long chain aliphatic alkenes with terminal double bond were nitrated in 95% yield (5a) whereas internal alkenes (5h and 5i) was giving moderate to good result. Traditionally, 1,5-cyclooctadiene or its analogues have been used as a very useful ligand in transition metal (Pd, Ni etc.) catalysis. By applying the reaction condition of the present invention on 1,5-cyclooctadiene as a substrate mono nitrated product was obtained selectively (5g). An ester group on a distant position of a terminal alkene (5c) was tolerated as well giving the nitro product in 60% isolated yield. Also compounds of natural product origin, such as (+)- limonene was nitrated in good yield (5e). In case of (+)-limonene, it was found that only terminal double bond was nitrated selectively. Interestingly, homoallylic analogue of styrene were also nitrated in acceptable yields (5j).

SCHEME 5 - Scope of aliphatic olefina

aIsolated yield of the E isomer as determined by the 1H NMR analysis; Olefin (0.5 mmol), AgN02 (1.5 mmol), TEMPO (0.2 mmol), 150 mg MS, 70 °C, DCE (2 mL); byield corresponds to E isomer only, ElZ ratio determined by GC-MS analysis of the reaction mixture; cisolated as a mixture of ElZ isomer; dfrom trans-4-octene, stereochemistry of the product was determined by COSY/NOESY analysis; "isolated as a mixture of regioisomers.
Even heterocyclic olefins (6a-6e) were nitrated in excellent yield (60-90%). Hetero olefins containing one and two heteroatoms were found to give corresponding nitro product by

applying the usual reaction condition. Both pyrazole and oxazole based olefins (6a and 6b) were nitrated as efficiently as furan (6c) and thiophene (6d and 6e) analogues.
SCHEME 6- Scheme of heterocyclic olefina

aIsolated yield of the E isomer as determined by the 1H NMR analysis; Olefin (0.5 mmol), AgN02 (1.5 mmol), TEMPO (0.2 mmol), 150 mg MS, 70 °C, DCE (2 mL). byield corresponds to E isomer only, E/Z ratio determined by GC-MS analysis of the reaction mixture; c01efin (0.16 mmol), AgN02 (0.6 mmol), TEMPO (0.1 mmol), 80 mg MS.
The reaction condition as described in the present invention was applied on several complex molecules to demonstrate the generality of method. Substrate, derived from cholestan-3-one of steroid cholesterol family, containing exo-cyclic double bond was nitrated in an excellent yield (7a, 93% yield). Also substrates derived from naturally occurring vitamin E (7e, 90%), testosterone (7c, 82%) and pregnenolone (7b) were nitrated in excellent yield. These examples clearly exhibit the beneficial aspects of the present invention and indicate that it can be applied in synthesis of large molecules which are of pharmacological significance and for SAR studies.


SCHEME 7- Nitration of complex molecular scaffoldsa
isolated yield of the £ isomer as determined by the1H NMR analysis; Olefin- AgNO2. TEMPO (in mmol) 7a 0.4: 1.2: 0.2; 7b 0.14: 0.45: 0.1; 7c 0.3: 1: 0.15; 7d 0.25: 0.75: 0.1; 7e 0.2: 1: 0.2; Stereochemistry of the product was determined by COSY/NOESY analysis.
The inventors of the present invention have successfully intercepted the proposed intermediate with norbornene as the substrate. From the crystal structure, formation of syn-adduct across the double bond by nitro group and TEMPO was clearly evident (Figure 1). However, steric demand of the bicyclic system probably inhibited further progress of the reaction.
The following examples are provided to better illustrate the claimed invention and are not to be interpreted in any way as limiting the scope of the invention. All specific materials and methods described below, in whole or in part, fall within the scope of the invention. These specific

components, materials, and methods are not intended to limit the invention, but merely to illustrate specific embodiments falling within the scope of the invention. One skilled in the art may develop equivalent materials and methods without the exercise of inventive capacity and without departing from the scope of the invention. It will be understood that many variations can be made in the procedures herein described while still remaining within the bounds of the invention. It is the intention of the inventors that such variations are included within the scope of the invention.
General Consideration and Experimental Section:
Reagent Information. Unless otherwise stated, all reactions were carried out under in screw cap reaction tubes. All the solvents were bought from Aldrich and were used as received. Silver Nitrite, Ferric Nitrate, tert-butyl nitrite and TEMPO were purchased from Aldrich/Alfa Aesar and Spectrochem respectively. Molecular sieves (4A; particle size 2-3 μ) were bought from Aldrich and were always kept in oven in small amount before use. Olefins corresponding to entries 4a, 4c, 4f, 5h and 5i were bought from Alfa Aesar. Olefins corresponding to entries 4b, 4d, 4e, 4g, 4h, 4j-4o, 5a-5e and 5g were bought from Aldrich. Other olefins were synthesized from commercially available compounds by Wittig reaction, esterification, amide synthesis etc. For column chromatography, silica gel (60-120 mesh or 100-200 mesh) obtained from SRL Co. was used. A gradient elution using pet ether and ethyl acetate was performed, based on Merck aluminium TLC sheets (silica gel 6OF254).
1 13
Analytical Information. All compounds are characterized by H NMR, C NMR spectroscopy, Gas chromatography mass spectra (GC-MS) and HRMS. Copies of the 1H NMR, 13C NMR can be found in the Supporting Information. Unless otherwise stated, all Nuclear Magnetic Resonance spectra were recorded on a Bruker 400 MHz instrument. All H NMR experiments are reported in units, parts per million (ppm), and were measured relative to the signals for residual chloroform (7.26 ppm) in the deuterated solvent, unless otherwise stated. All 13C NMR spectra were reported in ppm relative to deuterochloroform (77.23 ppm), unless otherwise stated, and all were obtained with 1H decoupling. All GC analyses were performed on a Agilent 7890A GC system with an FID detector using a J & WDB-1 column (10 m, 0.1 mm I.D.) using n-decane as the internal standard. All GC-MS analyses were done by Agilent 7890A GC system connected with 5975C inert XL EI/CI MSD (with triple axis detector). High-resolution mass spectra (HRMS) were recorded on a micro-mass ESI TOF (time of flight) mass spectrometer. Melting point of the compounds was determined using a Buchi B-545 melting point apparatus.


Optimization details for nitroolefin synthesis:
Table 1: Optimization by varying different nitrating agent.

Entry Nitrating Agents TEMPO GC Yield (%) *
1 AgN02 0.2 99
2 Fe(N03)3.9H20 0.1 95
3 Bi(N03)3.5H20 0.1 74
4 Co(N03)2.6H20 0.1 37
5 Na3Co(N02)6 0.1 22
6 NaN02 0.1 0
7 AgN03 0.1 0
8 Ni(N03)2.6H20 0.1 0

Table 2 : Optimization by varying different Solvents.

Entry Solvents GC Yield (%)
1 DCE 46
2 Benzene 45
3 DCM 44
4 DMSO 43
5 Acetonitrile 33
6 CHC13 29
7 Dioxane 12
8 p-Xylene 20
9 o-Xylene 19
10 THF 6
11 DMF 5
12 Toluene 15
13 Cyclohexane 11
Table 3: Optimization by varying different Solvents with Fe(NO3)3.9H20


Entry Solvents GC Yield (%)
1 DCE 95
2 Benzene 80
3 Dioxane 62
4 THF 1
5 DMF 43
6 Toluene 68
7 Cyclohexane 63
Table 4: Optimization by varying amount of AgNO2 and TEMPO.

Entry AgNO2 (mmol) K2S2O8 (mmol) TEMPO (mmol) GC Yield ( %)
1 1.0 0.5 0.2 82
2 1.0 - 0.2 85
3 1.0 0.5 0.1 78
4 1.0 - 0.1 81
5 1.5 - 0.1 85
6 1.5 - 0.2 99

Table 5: Optimization by varying amount of BuNO2 and TEMPO.

Entry tBuN02 (mmol) TEMPO (mmol) GC Yield ( % )
1 1.0 0.1 63
2 1.0 0.2 87
3 1.0 0.3 88
4 1.5 0.1 65
■ 5 1.5 0.2 60
6 1.5 0.3 56
Table 6: Optimization by varying different Solvents with lBuNO2

Entry Solvents GC Yield (%)
1 DCE 61
2 Benzene 35
3 Dioxan 69
4 THF 58
5 DMF 31

6 Toluene 42
7 MeCN 63
General Procedure A for nitration of olefins with AgNO2 and TEMPO under using DCE as the solvent
To an oven-dried screw cap test tube charged with a magnetic stir-bar was added AgNO2 (3 equiv.), TEMPO (0.4 equiv.) and oven-dried molecular sieves (4 A, 150 mg). Also depending on the physical state of the starting olefins, solid compounds were weighed along with the reagents and liquid olefins were added. The olefin (if it was liquid) and solvent (DCE, 2 mL) were added by microliter syringe and laboratory syringe respectively. The tube was placed in a preheated oil bath at 70 °C and the reaction mixture was stirred vigorously for 12h. Then the reaction mixture was cooled to room temperature. The reaction mixture was filtered through a celite bed filter with ethyl acetate as the washing solvent. Finally organic extract was concentrated and was purified by column chromatography using silica gel (60-120/100-200 mesh size) and PET-ether / ethyl acetate as the eluent.
General Procedure D for nitration of olefins with Fe(NO3)3-9H2O and TEMPO using DCE as the solvent
To an oven-dried screw cap test tube charged with a magnetic stir-bar was added Fe(NO3)3.9H2O (2 equiv.), TEMPO (0.2 equiv.) and oven-dried molecular sieves (4 A, 150 mg). Also depending on the physical state of the starting olefins, solid compounds were weighed along with the reagents and liquid olefins were added under nitrogen atmosphere. The olefin (if it was liquid) and solvent (DCE, 2 mL) were added by microliter syringe and laboratory syringe respectively. The tube was placed in a preheated oil bath at 70 °C and the reaction mixture was stirred vigorously for 12h. Then the reaction mixture was cooled to room temperature. The reaction mixture was filtered through a celite bed filter with ethyl acetate as the washing solvent. Finally organic extract was concentrated and was purified by column chromatography using silica gel (60-120/100-200 mesh size) and PET-ether / ethyl acetate as the eluent.
General Procedure D for synthesis of olefins from corresponding aldehydes and ketones by Wittig reaction

To an oven-dried two neck round bottom flask (100 mL) charged with a magnetic stir-bar was added Wittig salt (methyl)triphenylphosphonium iodide (3 mmol, approximately 1200 mg). Then the RB flask was fitted with a reflux condenser which was attached with a nitrogen balloon through a two way glass take-off. Under nitrogen atmosphere, 15-20 mL solvent (dry benzene) was added with a laboratory syringe and the system was kept in ice bath. Approximately, 700-800 mg of potassium tert-butoxide was added quickly and the system was allowed to come to room temperature and was refluxed for one hour. Formation of the ylide can be visibly observed by its persistent yellow colour. After refluxing, the system was again allowed to come to room temperature and kept in an ice bath, followed by drop wise addition of the substrate dissolved in dry benzene. Then the system was kept in room temperature for 4-6 hours, and progress of the reaction was monitored by TLC and GC-MS analysis. Upon completion, the reaction was quenched by saturated solution of ammonium chloride and the organic layer was extracted with ethyl acetate several times. The organic layer was dried over oven-dried anhydrous sodium sulfate and evaporated under reduced pressure. The crude reaction mixture was purified with silica gel column chromatography (60-120 mesh) with PET-ether/ethyl acetate as the eluent.
Characteristic Data of Synthesized Nitroolefins:

(E)-β-Nitrostyrene. Nitration was done by general procedure A and B with styrene (0.5 mmol, 57 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); crystalline yellow solid; isolated yield: 95% (71 mg); 90% (67 mg). 1H NMR (400 MHz, Chloroform-d) 5 7.41 - 7.48 (m,2H), 7.48 -7.52 (m, 1H), 7.52 - 7.56 (m, 2H), 7.56- 7.64 (dd, J = 13.7, 1.1 Hz, 1H), 7.95 - 8.05 (dd, J= 13.7, 1.8 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) 5 129.29, 129.53, 130.17, 132.30, 137.22, 139.23. GC-MS (m/z): 149.1 [M]+. m. p. 57-58 °C.

(E)-l-methoxy-4-(2-nitrovinyI)benzene (Scheme 4, 4a). Nitration was done by general procedure A and B with 4-methoxystyrene (0.5 mmol, 67 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); crystalline yellow solid; isolated yield: 85% (76 mg); 74% (66 mg)1H NMR (400 MHz, Chloroform-d) δ 3.52 - 4.21 (s, 3H), 6.83 - 7.00 (d, J = 8.8 Hz, 2H), 7.43 - 7.47 (d, J= 2.0 Hz, 1H), 7.47 - 7.50 (m, 1H), 7.50 - 7.54 (s, 1H), 7.85 - 8.01 (d, J= 13.6 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 55.59, 114.97, 122.54, 131.28, 135.00, 139.13, 163.02. GC-MS (m/z): 179.1 [M]+. m. p. 57-58 °C


(E)-l-methyl-4-(2-nitrovinyl)benzene (Schema 4, 4b). Nitration was done by general procedure A and B with 4-methylstyrene (0.5 mmol, 66 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); yellow solid; isolated yield: 96% (78 mg); 88% (72 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.32 - 2.56 (s, 3H), 7.17 - 7.37 (m, 2H), 7.37 -7.52 (m, 2H), 7.52 - 7.68 (d, J= 13.7 Hz, 1H), 7.92 - 8.07 (d,J= 13.6 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 21.84, 127.41, 129.36, 130.30, 136.41, 139.35, 143.29. GC-MS (m/z): 163.1 [M]+ m. p. 106-107 °C.

(E)-4-(2-nitrovinyl)benzonitrile (Scheme 4, 4C). Nitration was done by general procedure A and B with 4-vinylbenzonitrile (0.5 mmol, 65 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); light yellow solid; isolated yield: 81% (71 mg); 77% (67 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.58 - 7.65 (d, J= 13.8 Hz, 1H), 7.65 - 7.71 (m, 2H), 7.71 - 7.81 (m, 2H), 7.95 - 8.05 (d, J= 13.7 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 115.38, 118.00, 129.59, 133.21, 134.52, 136.77, 139.63. GC-MS (m/z): 174.1 [M]+. m. p. 186-187 °C.

(E)-methyl 4-(2-nitrovinyl)benzoate (Scheme 4, 4d). Nitration was done by general procedure A with l-nitro-4-vinylbenzene (0.5 mmol, 66 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); yellow solid; isolated yield: 93% (86 mg). 1H NMR (400 MHz, Chloroform-d) 5 3.30 - 4.47 (s, 3H), 7.60 - 7.62 (s, 1H), 7.62 - 7.65 (m, 2H), 7.97 - 8.06 (d, J= 13.7 Hz, 1H), 8.06 - 8.14 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 5 52.71, 129.16, 130.64, 133.19, 134.35, 137.77, 138.85, 166.17. GC-MS (m/z): 207.1 [M]+. m. p. 176-178 °C.

(E)-l-chloro-4-(2-nitrovinyl)benzene (Scheme 4, 4e). Nitration was done by general procedure A and B with l-chloro-4-vinylbenzene (0.5 mmol, 63 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent:

ethyl acetate/ petroleum ether (2:98 v/v); crystalline light yellowish solid; isolated yield: 97% (89 mg); 85% (78 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.38 - 7.45 (m, 2H), 7.45 - 7.53 (m, 2H), 7.53 - 7.64 (d, J= 13.7 Hz, 1H), 7.90 - 8.01 (d, J= 13.7 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 128.65, 129.87, 130.42, 137.53, 137.85, 138.43, 77.51, 77.20, 76.88. GC-MS (m/z): 183.1 [M]+. m. p. 113-114 °C.

(E)-l-fluoro-4-(2-nitrovinyl)benzene (Scheme 4, 4f). Nitration was done by general procedure A with 1 -fluoro-4-vinylbenzene (0.5 mmol, 65 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:98 v/v); light yellow solid; isolated yield: 95% (79 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.09-7.21 (m, 2H), 7.51-7.55 (m, 1H), 7.55-7.60 (m, 2H), 7.88 -8.22(d,J = 13.7Hz, 1H). 13CNMR(101 MHz, Chloroform-d) 8 116.90, 117.12, 131.53, 137.04, 138.04, 166.41. GC-MS (m/z): 167.1 [M]+. m. p. 102-103 °C.

(E)-l-nitro-3-(2-nitrovinyl)benzene (Scheme 4, 4g). Nitration was done by general procedure A and B with l-nitro-3-vinylbenzerie (0.5 mmol, 75 μL, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (3:97 v/v); isolated yield: 97% (84 mg); 70% (68 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.65 - 7.70 (m, 1H), 7.70 - 7.72 (d, J= 3.4 Hz, 1H), 7.85 - 7.93 (dt, J =7.9, 1.4, 1.4 Hz, 1H), 7.98 - 8.13 (d, J= 13.7 Hz, 1H), 8.30 - 8.39 (ddd, J = 8.2, 2.2, 1.0 Hz, 1H), 8.39 - 8.47 (dt, J = 2.2, 1.1, 1.1 Hz, 1H). I3C NMR (101 MHz, Chloroform-d) δ 123.65, 126.36, 130.79, 131.96, 134.67, 136.46, 139.42, 148.92. GC-MS (m/z): 194.1 [M]+. m. p. 125-126 °C.

(E)-3-(2-nitrovinyl)benzaldehyde (Scheme 4, 4h). Nitration was done by general procedure A and B with 3-vinylbenzaldehyde (0.5 mmol, 66 μE, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); light yellow solid; isolated yield: 82% (73 mg); 78% (69 mg). ]H NMR (400 MHz, Chloroform-d) 8 7.67 (m, 1H), 7.70-7.71 (d, J= 4 Hz

1H), 7.83 (dt, J= 8.0, 4 Hz, 1H), 7.87 - 7.95 (dt, J= 8.0, 4 Hz, 1H), 8.09 (d, J= 12Hz, 1H), 10.08 (s, 1H), 13C NMR (101 MHz, CDC13) δ 76.91, 77.23, 77.55, 123.65, 126.36, 130.79, 131.96, 134.67, 136.46, 139.42, 148.92. I3C NMR (101 MHz, Chloroform-d) δ 129.73, 130.39, 131.26, 133.01, 134.54, 137.31, 137.60, 138.54, 191.26. GC-MS (m/z): 177.1 [M]+. m. p. 91-92 °C.

(E)-N-(3-(2-nitrovinyl)phenyl)tetradecanamide (Scheme 4, 4i). Nitration was done by general procedure A with N-(3-viny]phenyl)tetradecanamide (0.25 mmol, 80 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (20:80 v/v); crystalline light yellowish solid; isolated yield: 75% (70 mg). 1H NMR (400 MHz, Chloroform-d) 8 0.80 - 0.95 (m, 3H), 1.07 - 1.54 (s, 20H), 1.68 - 1.80 (p, J = 7.6, 7.6, 7.5, 7.5 Hz, 2H), 2.31 - 2.44 (m, 2H), 7.27 - 7.29 (t, J= 1.3, 1.3 Hz, 1H), 7.30 - 7.34 (s, 1H), 7.35 - 7.43 (t, J= 7.9, 7.9 Hz, 1H), 7.46 - 7.54 (dd, J= 2.2, 1.1 Hz, 1H), 7.55 - 7.63 (d,J= 13.7 Hz, 1H), 7.91 - 8.00 (d, J= 13.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 14.34, 22.90, 25.71, 29.47, 29.57, 29.59, 29.69, 29.83, 29.86, 29.89, 32.13, 37.99, 119.93, 123.16, 125.12, 130.14, 131.12, 137.76, 138.96, 139.21, 172.03. HRMS (ESI): calcd. for C22H35N2O3: 375.2648, found: 375.2630. m. p. 121-122 °C.

(E)-l-methoxy-2-(2-nitrovinyl)benzene (Scheme 4, 4j). Nitration was done by general procedure A with 2-methoxystyrene (0.5 mmol, 66 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (3:97 v/v); yellow solid; isolated yield: 85% (76 mg). 1H NMR (400 MHz, Chloroform-d) 8 3.47 - 4.33 (s, 3H), 6.88 - 7.09 (m, 2H), 7.36 - 7.53 (m, 2H), 7.77 -7.99 (d,J= 13.6 Hz, 1H), 8.07-8.19 (d,J= 13.5 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 55.75, 111.47, 119.18, 121.20, 132.60, 133.61, 135.65, 138.32 ,159.60. GC-MS (m/z): 179.1. [M]+. m. p. 84 °C.

(E)-l-bromo-2-(2-nitrovinyl)benzene (Scheme 4, 4k). Nitration was done by general procedure A and B with l-bromo-2-vinylbenzene (0.5 mmol, 65 L) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (3:97 v/v); crystalline light yellowish solid; isolated yield: 92% (104 mg); 77% (88 mg). 1H NMR (400 MHz, Chloroform-d) 5 7.29 - 7.45 (m, 2H),

7.50 - 7.56 (d, J= 13.6 Hz, 1H), 7.56 - 7.60 (m, 1H), 7.63 - 7.75 (m, 1H), 8.33 - 8.45 (d, J= 13.6 Hz, 1H). 13CNMR(101 MHz, Chloroform-d) 8 126.53, 128.27, 128.63, 130.43, 133.15, 134.16, 137.78, 138.95. GC-MS (m/z): 228.1 [M]+. m.p. 88-89 °C.

(E)-2-(2-nitrovinyl)naphthaIene (Scheme 4, 41). Nitration was done by general procedure A with 2-vinylnaphthalene (0.5 mmol, 77 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (3:97v/v); yellowish solid; isolated yield: 88% (106 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.41 - 7.63 (tdd, J= 11.1,11.1, 6.4, 1.7 Hz, 3H), 7.63 - 7.76 (dd, J= 13.6, 4.0 Hz, 1H), 7.76 - 7.92 (m, 3H), 7.92 - 8.04 (d, J= 6.6 Hz, 1H), 8.04 - 8.18 (m, 1H). 13C NMR (101 MHz, Chloroform-d) 5 76.91, 77.23, 77.54, 123.41, 127.40, 127.62, 128.06, 128.53, 128.96, 129.45, 132.45, 133.22, 135.00, 137.19, 139.35. GC-MS (m/z): 199.1 [M]+. m.p. 128-130 °C.

(E)-(l-nitroprop-l-en-2-yl)benzene (Scheme 4, 4m). Nitration was done by general procedure A with prop-l-en-2-ylbenzene (0.5 mmol, 65 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether(2:98 v/v); yellow solid; isolated yield; 94 % (77 mg); 5J % (42 mg). lH NMR (400 MHz, Chloroform-d) δ 2.29 - 3.07 (d,J= 1.5 Hz, 3H), 7.29 - 7.33 (q, J = 1.4, 1.4, 1.4 Hz, 1H), 7.41 -7.49 (m,5H). 13CNMR(101 MHz, Chloroform-d) δ 18.77, 127.00, 129.19, 130.55, 136.47, 138.43, 150.19. GC-MS (m/z): 163.1 [M]+. m. p. 176-178 °C.

(Z)-(2-nitroprop-l-enyl)benzene (Scheme 4, 4n). Nitration was done by general procedure A with (Z)-prop-l-enylbenzene (0.5 mmol, 65 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (3:97 v/v); yellow liquid; isolated yield: 66% (54 mg). 1H NMR (400 MHz, Chloroform-d) δ 2.42 - 2.51 (d, J = 1.1 Hz, 3H), 7.37 - 7.52 (m, 5H), 8.05 - 8.15 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 14.25, 128.16, 129.10, 130.12, 132.61, 133.76, 147.94. GC-MS (m/z): 163.1 [M]+. HRMS (ESI): calcd. for C9H10NO2: 164.0712, found: 164.0713.


(2-nitroethene-l,l-diyl)dibenzene (Scheme 4, 4o). Nitration was done by general procedure A with ethene-l,l-diyldibenzene as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:98 v/v); yellow liquid; isolated yield: 95% (63 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.19 - 7.25 (m, 2H), 7.27 - 7.32 (m, 2H), 7.36 - 7.40 (m, 1H), 7.40 - 7.50 (m, 6H). 13C NMR (101 MHz, Chloroform-d) δ 128.68, 128.98, 129.06, 129.10, 129.50, 131.09, 134.57, 135.71, 137.26, 150.68. GC-MS (m/z): 225.1 [M]+.

(E)-5-nitro-6-(2-nitrovinyl)benzo[d][l,3]dioxole (Scheme 4, 4p). Nitration was done by general procedure A with 5-nitro-6-vinylbenzo[d][l,3]dioxole (0.5 mmol, 96 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (30:70 v/v); yellowish solid; isolated yield: 70% (83 mg). 1H NMR (400 MHz, Chloroform-d) 5 6.15 - 6.30 (s, 2H), 6.88 -6.98 (s, 1H), 7.31 - 7.43 (d,J= 13.4 Hz, 1H), 7.61 - 7.69 (s, 1H), 8.41 - 8.63 (d, J= 13.4 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 104.13, 106.61, 107.79, 122.51, 135.90, 139.41, 143.75, 150.56, 152.59. GC-MS (m/z): 238.1 [M]+. m.p. 110-111 °C.

(E)-l,3,5-trimethyl-2-(2-nitrovinyl)benzene (Scheme 4, 4q). Nitration was done by general procedure A with l,3,5-trimethyl-2-vinylbenzene (0.5 mmol, 80 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether; yellowish solid; isolated yield: 93% (89 mg). 'H NMR (400 MHz, Chloroform-d) 5 2.25 - 2.35 (s, 3H), 2.35 - 2.47 (s, 6H), 6.83 - 7.06 (s, 2H), 7.28 - 7.39 (d, J = 13.9 Hz, 1H), 8.22 - 8.35 (d, J = 13.9 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) 8 21.42, 21.75, 125.95, 130.09, 136.79, 138.67, 139.88, 141.07. GC-MS (m/z): 191.1 [M]+. m.p. 123-124 °C.

(E)-l-(2-nitrovinyl)-2-vinylbenzene (Scheme 4, 4r). Nitration was done by general procedure A with 1,2-divinylbenzene (0.23 mmol, 30 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; yellowish oil; isolated yield: 70% (30 mg). 1H NMR (400 MHz, Chloroform-d) δ 5.48 - 5.58 (dd, J= 11.0, 1.0 Hz, 1H), 5.62 - 5.71 (dd, J= 17.3, 1.0 Hz, 1H), 6.98 - 7.07 (dd, .7=17.3, 11.0 Hz, 1H), 7.30-7.40 (td, J = 7.5, 7.5, 1.4 Hz, 1H), 7.42 -7.59 (m, 4H), 8.28 -8.42 (d,J= 13.5 Hz, 1H). GC-MS (m/z): 175.1 [M]+.


(E)-l-nitrodec-l-ene (Scheme 5, 5a). Nitration was done by general procedure A and B with dec-1-ene (0.5 mmol, 94 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); reddish orange liquid; isolated yield: 95% (88 mg); 71% (66 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.81 - 0.95 (h,J= 3.5, 3.5, 3.5, 3.4, 3.4 Hz, 5H), 1.20 - 1.39 (m, 8H), 1.46 - 1.60 (dq, J= 14.9, 7.5, 7.2, 7.2 Hz, 2H), 2.22 - 2.31 (qd, J= 7.6, 7.6, 7.5, 1.6 Hz, 2H), 6.94 - 7.02 (dt, J = 13.4, 1.6, 1.6 Hz, 1H), 7.22 - 7.34 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 14.24, 22.79, 27.87, 28.62, 29.25, 29.37, 31.94, 139.68, 143.04. HRMS (ESI): calcd. for C0H20NO2: 186.1494, found: 186.1501.

(E)-(2-nitrovinyl)cycIohexane (Scheme 5, 5b). Nitration was done by general procedure A and B with vinylcyclohexane (0.5 mmol, 68 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (x:y v/v); orange liquid; isolated yield: 90% (70 mg); 65% (46 mg). 1H NMR (400 MHz, Chloroform-d) δ 1.1-1.3 (m, 6H), 1.74-1.83 (m 4H), 2.2-2.3(m, 1H), 6.89-6.94 (m, 1H), 7.20 (m,lH). 13CNMR(101 MHz, Chloroform-d) δ 25.59, 25.75, 31.56, 37.70, 138.39, 147.49.

(E)-methyl ll-nitroundec-10-enoate (Scheme 5, 5c). Nitration was done by general procedure A with methyl undec-10-enoate (0.5 mmol, 112 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); orange liquid; isolated yield: 58% (70 mg). 1H NMR (400 MHz, Chloroform-d) δ 1.22 - 1.42 (m, 14H), 1.57 - 1.75 (m, 4H), 2.11 - 2.47 (m, 5H), 2.49 -2.67 (m, 1H), 3.57-3.79 (s,3H), 6.87-7.14 (dt,J= 13.4, 1.5, 1.5 Hz, 1H), 7.14 - 7.38 (dt, J = 13.3, 7.4, 7.4 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 24.83, 27.06, 27.66, 28.39, 28.78, 28.99, 30.04, 33.98, 51.42, 116.84, 139.56, 142.75, 174.20. GC-MS (m/z): 212.1 [M]+. From GC-MS analysis of reaction mixture, it was observed that 20% starting material left unreacted.

(E)-10-bromo-l-nitrodec-l-ene (Scheme 5, 5d). Nitration was done by General Procedure A and B with 10-bromodec-l-ene (0.5 mmol, 100 μX) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl

acetate/ petroleum ether (5:95 v/v); yellow liquid; isolated yield: 44% (33 mg); 52% (39 mg). 1H NMR (400 MHz, Chloroform-d) 8 1.18 - 1.47 (m, 15H), 1.47 - 1.56 (m, 2H), 1.57 - 1.75 (m, 9H), 1.75 - 1.95 (m, 5H), 2.19 - 2.33 (qd, J= 7.5, 7.5, 7.4, 1.6 Hz, 2H), 3.36 - 3.45 (t, J= 6.8, 6.8 Hz, 3H), 6.94-7.02 (dt, J- 13.4, 1.6, 1.6 Hz, 1H), 7.21-7.33 (dt, J= 13.4, 7.4, 7.4 Hz, 1H).

(R,E)-l-methyl-4-(l-nitroprop-l-en-2-yl)cyclohex-l-ene (Scheme 5, 5e). Nitration was done by general procedure A with ((R)-l-methyl-4-(prop-l-en-2-yl)cyclohex-l-ene (0.5 mmol, 85 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); light yellowish liquid; isolated yield: 69% (62 mg). 1H NMR (400 MHz, Chloroform-d) 5 1.63 - 1.68 (tq, J = 1.7, 1.7, 1.0, 0.9, 0.9 Hz, 5H), 1.69- 1.76 (m, 1H), 1.82- 1.86 (d, J = 1.4 Hz, 1H), 1.90-2.17 (m, 3H), 2.20 - 2.24 (d, J=1A Hz, 3H), 5.36 - 5.43 (dtd, J= 4.8, 2.4, 2.4, 1.3 Hz, 1H), 6.95 -6.98 (m, 1H). 13C NMR (101 MHz, Chloroform-d) 8 17.21, 23.54, 27.01, 29.95, 30.02, 42.24, 119.35, 134.30, 135.16, 157.27. HRMS (ESI): calcd. for C10H16NO2: 182.1181, found: 182.1173.


(lE,5Z)-l-nitrocycloocta-l,5-diene (Scheme 5, 5g). Nitration was done by general procedure A with (lZ,5Z)-cycloocta-l,5-diene (0.5 mmol, 54 uL) as the substrate. Pure nitrated product was
(1s,4R,E)-l-isopropyl-4-methyl-2-(nitromethylene)cyclohexane (Scheme 5, 5f). Nitration was done by general procedure A with (1S,4R)- l-isopropyl-4-methyl-2-methylenecyclohexane (0.5 mmol, 76 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); light yellowish liquid; isolated yield: 35% (30 mg). 1H NMR (400 MHz, Chloroform-d) 8 0.74 - 1.12 (m, 9H), 1.13 - 2.23 (m, 7H), 2.45 - 2.63 (dd,J = 13.1, 7.3 Hz, 1H), 2.77 - 3.08 (ddt,J = 13.0, 4.7, 0.9, 0.9 Hz, 1H), 6.82 - 7.00 (q,J = 1.0, 1.0, 1.0 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) 5 19.83, 20.29, 21.86, 27.20, 27.49, 30.79, 33.58, 34.75, 50.66, 123.22, 133.93, 157.26. HRMS (ES1): calcd. for C11H20NO2: 198.1494, found: 198.1503.

isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); reddish orange liquid; isolated yield: 53% (40 mg). 1H NMR (400 MHz, Chioroform-d) 6 2.40 - 2.55 (dtdd, J= 12.2, 6.1, 6.1, 3.0, 1.2 Hz, 4H), 2.55 -2.68 (q, J= 6.4, 6.3, 6.3 Hz, 2H), 2.95 - 3.10 (m, 2H), 5.47 - 5.63 (m, 2H), 7.29 - 7.40 (t, J = 6.3, 6.3 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 25.81, 26.47, 26.86, 27.23, 127.83, 128.78, 135.41, 151.68. HRMS (ESI): calcd. for CsH,2NO2: 154.0868, found: 154.0867.

(E)-4-nitrooct-4-ene (Scheme 5, 5h). Nitration was done by general procedure A and B with trans-4-octene (0.5 mmol, 56 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: petroleum ether; yellowish liquid; isolated yield: 51% (40 mg); 53% (42 mg). ]H NMR (400 MHz, Chloroform-d) δ 0.75 - 1.04 (m, 7H), 1.43 - 1.65 (ddt,J= 14.7, 7.3, 3.5, 3.5 Hz, 3H), 2.13-2.29 (q,J= 7.6, 7.6, 7.6 Hz, 2H), 2.44-2.66 (m, 2H), 7.00 -7.18 (t, J= 7.9, 7.9 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 13.78, 13.99, 14.27, 21.39, 22.04, 22.84, 28.35, 30.13, 31.78, 136.55, 151.90. Stereochemistry of the final product was determined by COSY/NOESY analysis. HRMS (ESI): calcd.for C8H15NO2: 180.1000, found: 180.0999.

(E)-2-nitrohex-2-ene (Scheme 5, 5i). Nitration was done by general procedure A with cis-2-hexene (0.5 mmol, 63 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: petroleum ether; light yellowish liquid; isolated yield (mixture of regioisomers): 62% (40 mg).

(E)-(4-nitrobut-3-enyl)benzene (Scheme 5, 5j). Nitration was done by general procedure A with but-3-enylbenzene (0.5 mmol, 66 uL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); dark reddish orange liquid; isolated yield: 57% (50 mg). 1H NMR (400 MHz, Chloroform-d) δ 2.45 - 2.55 (qd, J= 7.5, 7.2, 7.2, 1.6 Hz, 2H), 2.70 - 2.78 (t, J= 7.5, 7.5 Hz, 2H), 6.79 - 6.96 (dt, J = 13.4, 1.6, 1.6 Hz, 1H), 7.08 - 7.13 (m, 2H), 7.13 - 7.20 (m, 2H), 7.20 - 7.25 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 5 30.13, 33.93, 126.63, 128.35, 128.74, 139.68, 139.99, 141.56. GC-MS (m/z): 177.1 [M]+.


(E)-(3-methyl-4-nitrobut-3-en-l-ynyl)benzene (Scheme 5, 5k). Nitration was done by general procedure A with (3-methylbut-3-en-l-ynyl)benzene (0.35 mmol, 50 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100— 200). Eluent: petroleum ether; orange-yellow liquid; isolated yield: 30% (20 mg). 1H NMR (400 MHz, Chloroform-d) δ 2.35 - 2.73 (d, J= 1.6 Hz, 3H), 7.32 - 7.34 (q, J= 1.6, 1.5, 1.5 Hz, 1H), 7.35 - 7.45 (m, 3H), 7.46 - 7.54 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 6 20.29, 87.54, 100.02, 121.46, 128.83, 130.25, 132.33, 133.60, 141.34. HRMS (ESI): calcd. for C11H10N02: 188.0712, found: 188.0713. GC-MS (m/z): 175.1 [M]+.

((lE,3E)-4-nitrobuta-l,3-dienyl)benzene. Nitration was done by general procedure A with (E)-buta-l,3-dienylbenzene (0.5 mmol, 100 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: petroleum ether; yield: 10% (9 mg). 1H NMR (400 MHz, Chloroform-d) 8 6.79 - 6.93 (m, 1H), 7.08-7.18 (dd,J = 15.5, 3.0 Hz, 1H), 7.18 - 7.25 (dd,/= 13.1, 2.0 Hz, 1H), 7.34 - 7.53 (m, 5H), 7.69-7.81 (m, 1H). GC-MS (m/z): 175.1 [M]+.

(E)-(4-nitrobuta-l,3-diene-l,l-diyl)dibenzene (Scheme 5, 5m). Nitration was done by general procedure A with buta-l,3-diene-l,l-diyldibenzene (0.5 mmol, 103 uE) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: petroleum ether; dark orange liquid; isolated yield: 10% (12 mg). 'H NMR (400 MHz, Chloroform-d) 5 6.73 - 6.85 (m, 1H), 7.16 - 7.23 (m, 2H), 7.28 - 7.40 (m, 6H)5 7.42 -7.49 (dd, J=5.0, 1.8 Hz, 3H), 7.63 - 7.74 (dd,J = 13.0, 12.1 Hz, 1H). ,3C NMR (101 MHz, Chloroform-d) 5 119.71, 128.68, 128.75, 128.79, 129.40, 129.96, 130.56, 137.29, 137.82, 139.65, 140.73, 157.34. GC-MS (m/z): 251.1 [M]+


(E)-3-methyl-4-(2-nitrovinyl)-l-phenyl-lH-pyrazole (Scheme 6, 6a). Nitration was done by general procedure A with 3-methyl-l-phenyl-4-vinyl-lH-pyrazole (0.5 mmol, 92 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (6:94 v/v); yellow solid; isolated yield: 90% (100 mg). 1H NMR (400 MHz, Chloroform-d) 8 2.46 - 2.52 (s, 3H), 7.30 - 7.40 (m, 1H), 7.44 - 7.53 (m, 3H), 7.62 - 7.72 (m, 2H), 7.98 - 8.09 (dd, J= 13.7, 0.5 Hz, 1H), 8.12 - 8.20 (s, 1H). 13C NMR (101 MHz, Chloroform-d) 6 13.51, 113.63, 119.50, 127.74, 129.00, 129.88, 130.20, 135.13, 139.17, 151.47. HRMS (ESI): calcd. for C12H12N3O2: 230.0930, found: 230.0923. m.p. 143-144 °C.

(E)-3-(2-nitrovinyl)-5-phenylisoxazole (Scheme 6, 6b). Nitration was done by general procedure A with 5-phenyl-3-vinylisoxazole (0.5 mmol, 86 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (6:94 v/v); creamy solid; isolated yield: 80% (87 mg). 1H NMR (400 MHz, Chloroform-d) δ 6.68 - 6.77 (s, 1H), 7.43 - 7.58 (m, 3H), 7.63 - 7.74 (d,J = 13.8 Hz, 1H), 7.75 - 7.89 (m, 2H), 7.95 - 8.07 (d, J= 13.8 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 97.69, 126.18, 126.60, 129.45, 130.33, 131.29, 142.19, 156.44, 172.13. HRMS (ESI): calcd. for C1H9N2O3: 217.0613, found: 217.0615. m. p. 186-187 °C.

(E)-4-(2-nitrovinyl)dibenzo[b,d]furan (Scheme 6, 6c). Nitration was done by general procedure A with 4-vinyldibenzo[b,d]furan (0.5 mmol, 97 μL, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100— 200). Eluent: ethyl acetate/ petroleum ether (0.2:99.8 v/v); greenish yellow solid; isolated yield: 76% (90 mg). 1H NMR (400 MHz, Chloroform-d) 8 7.35 - 7.46 (m, 2H), 7.49 - 7.57 (dtd, J = 7.2, 4.4, 4.1, 1.3 Hz, 2H), 7.61 - 7.68 (dt, 7= 8.3, 0.9, 0.9 Hz, 1H), 7.91 - 7.99 (m, 1H), 7.99 -8.10 (dd, J =7.7, 1.2 Hz, 1H), 8.09-8.21 (d,J= 13.6 Hz, 1H), 8.24 - 8.36 (d, J= 13.7 Hz, 1H).

13C NMR (101 MHz, Chloroform-d) δ 76.91, 77.23, 77.54, 112.18, 115.47, 121.06, 123.24, 123.60, 123.86, 124V.48, 125.52, 128.27, 130.66, 134.36, 139.91, 154.44, 156.21. HRMS (ESI): calcd. for C14H10NO3: 240.0661, found; 240,0668. m. p. 123-124 °C.

(E)-2-bromo-5-(2-nitrovinyl)thiophene (Scheme 6, 6d). Nitration was done by general procedure A with 2-bromo-5-vinylthiophene (0.16 mmol, 30 uE, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (0.5:99.5 v/v); dark golden yellow solid; isolated yield: 81% (30 mg). 1H NMR (400 MHz, Chloroform-d) 8 7.09 - 7.15 (d, J = 3.9 Hz, 1H), 7.17 - 7.23 (dq, J= 4.0, 0.6, 0.6, 0.6 Hz, 1H), 7.33 - 7.42 (d, J= 13.4 Hz, 1H), 7.98 - 8.07 (dd, J = 13.4, 0.6 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) 5 119.82, 131.32, 132.07, 135.29, 135.38, 135.60. HRMS (ESI): calcd. for C6H5N02SBr: 233.9224, found: 233.9224.

(E)-3-(2-nitrovinyI)benzo[6]thiophene (Scheme 6, 6e). Nitration was done by general procedure A with 3-vinylbenzo[b]thiophene (0.5 mmol, 80 μL, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100— 200). Eluent: ethyl acetate/ petroleum ether (0.5:99.5 v/v); dark orange solid; isolated yield: 59% (60 mg). 1H NMR (400 MHz, Chloroform-d) δ 7.40 - 7.55 (m, 2H), 7.65 - 7.76 (d, J = 13.7 Hz, 1H), 7.85 - 7.95 (m, 3H), 8.18 - 8.29 (dd, J= 13.7, 0.7 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 122.06, 123.39, 125.75, 125.79, 127.12, 131.10, 133.09, 136.45, 136.68, 140.54. HRMS (ESI): calcd. for C10H8NO2S: 206.0276, found: 206.0279. m. p. 112-113 °C.

(8R,9S,10S,13,R,14S,17R,E)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-3-(nitromethylene)hexadecahydro-lH-cyclopenta[a]phenanthrene (Scheme 7, 7a). Nitration was done by general procedure A with (87,95,10S,,13R,145,17R)-10,13-dimethyl-3-methyIene-17-((R)-6-methylheptan-2-yl)hexadecahydro-lH-cyclopenta[a]phenanthrene (0.4 mmol, 154 mg)

as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (0.5:99.5 v/v); creamy white solid; isolated yield: 93% (160 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.54 - 0.78 (m, 5H), 0.78 - 1.20 (m, 23H), 1.20 - 1.41 (m, 4H), 1.42 - 1.63 (m, 3H), 1.63 - 1.74 (dq, J= 13.2, 3.6, 3.4, 3.4 Hz, 1H), 1.74 - 2.04 (m, 4H), 2.04 - 2.27 (m, 2H), 2.27 - 2.46 (m, 1H), 6.80 - 7.00 (q, J = 1.8, 1.8, 1.8 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) 5 12.08, 12.29, 18.87, 21.39, 22.78, 23.04, 24.03, 24.38, 28.23, 28.42, 29.13, 31.50, 32.06, 35.54, 35.99, 36.35, 36.84, 39.31, 39.71, 39.89, 40.09, 42.79, 48.32, 54.27, 56.42, 56.50, 132.16, 156.18. Stereochemistry of the final product was determined by COSY/NOESY analysis. HRMS (ESI): calcd. for C28H47NO2: 430.3685, found: 430.3676. m. p. 80-81 °C.

(8S,95,10R,135,145,17S)-10,13-dimethyl-17-((E)-l-nitroprop-l-en-2-yI)-2,3,4,7,8,9,10,ll,12,13,14,15,16,17-tetradecahydro-lH-cyclopenta[a]phenanthren-3-yl acetate (Scheme 7, 7b). Nitration was done by general procedure A with (85,95,1 OR, 135, 145,17R)-10,13-dimethyl-17-(prop-1 -en-2-yl)-
2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate (0.14 mmol, 50 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (20:80 v/v); creamy white solid; isolated yield: 40% (20 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.43-0.75 (d, J= 15.0 Hz, 2H), 0.77-1.08 (m, 4H), 1.08 - 1.37 (m, 4H), 1.37 - 1.67 (m, 3H), 1.67 - 1.95 (m, 3H), 1.95 - 2.16 (m, 3H), 2.16 - 2.43 (dd, J= 31.4, 3.4 Hz, 4H), 4.51-4.71 (m, 1H), 5.33-5.44 (dd, J =4.7, 2.3 Hz, 1H), 6.94 - 7.06 (t, J= 1.3, 1.3 Hz, 1H), 7.22 - 7.31 (d, J = 3.2 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 13.30, 19.48, 20.37, 21.08, 21.60, 24.44, 24.94, 27.86, 31.81, 32.25, 36.76, 37.12, 38.21, 38.51, 45.46, 50.11, 56.63, 58.43, 73.96, 122.34, 136.46, 139.90, 153.81, 170.73. HRMS (ESI): calcd. for C24H36NO4: 402.2644, found: 402.2635.


(8R,9S,10R,13S,14S,17S)-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-lH-cyclopenta[a]phenanthren-17-yl 4-((E)-2-nitrovinyl)benzoate (Scheme
7, 7c). Nitration was done by general procedure A with (8R,9S,10R,13S,14S,17S)-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,ll,]2,13,14,15,16,17-tetradecahydro-lH-
cyclopenta[a]phenanthren-17-yl 4-vinylbenzoate (0.3 mmol, 125 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl acetate/ petroleum ether (30:70 v/v); light yellowish solid; isolated yield: 82% (110 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.91 - 1.10 (m, 5H), 1.10- 1.35 (m, 5H), 1.35 - 1.53 (m, 2H), 1.53-1.81 (m, 6H), 1.81 - 1.96 (m, 2H), 1.97- 2.09 (m, 1H), 2.23 - 2.51 (m, 4H), 4.02 - 4.23 (q, J= 7.1, 7.1, 7.1 Hz, 1H), 4.78 - 4.96 (dd, J= 9.2, 7.7 Hz, 1H), 5.64 -5.82 (m, 1H), 7.48 - 7.54 (d, J = 8.0 Hz, OH), 7.59 - 7.66 (m, 3H), 7.72 - 7.76 (d, J= 8.7 Hz, OH), 7.99 - 8.05 (d, J= 13.9 Hz, 1H), 8.07 - 8.12 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 5 12.54, 17.63, 20.75, 23.81, 27.86, 31.69, 32.93, 34.13, 35.64, 35.92, 36.93, 38.82, 43.16, 50.48, 53.89, 83.77, 124.21, 129.16, 130.60, 133.72, 134.29, 137.81, 138.82, 165.56, 171.02, 199.66. HRMS (ESI): calcd. for C28H34NO5: 464.2437, found: 464.2423. m. p. above 200 °C.

(5R)-2-methyl-5-(prop-l-en-2-yl)cyclohex-2-enyl 4-((E)-2-nitrovinyI)benzoate (Scheme 7, 7d). Nitration was done by general procedure A with (5R)-2-methyl-5-(prop-l-en-2-yl)cyclohex-2-enyl 4-vinylbenzoate (0.25 mmol, 71 μL) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl acetate/ petroleum ether (0.5:99.5 v/v); isolated yield: 67% (55 mg). 1H NMR (400 MHz, Chloroform-d) δ 1.61 - 1.91 (d, J= 13.3 Hz, 7H), 1.91 - 2.26 (m, 2H), 2.26 - 2.58 (dddd, J = 45.0,23.3, 11.7, 4.9 Hz, 2H), 4.72-4.88 (m, 1H), 5.51 - 5.67 (m, 1H), 5.70 - 5.83 (q, J= 6.0, 6.0, 5.1 Hz, 1H), 5.83 - 5.96 (m, 1H), 7.62 - 7.82 (d, J= 9.0 Hz, 3H), 8.03 - 8.13 (d, J = 13.1 Hz, 1H), 8.14 - 8.25 (d, J= 7.3 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) 8 18.57, 20.44, 30.49, 33.24, 35.55, 39.72, 71.54, 108.93, 126.00, 127.95, 128.57, 130.07, 132.11, 133.14,


133.62, 137.23, 138.29, 148.05, 164.82. HRMS (ESI): calcd. for C19H22NO4: 328.1549, found: 328.1541.
(R)-2,5,7,8-tetramethyl-6-(4-((E)-2-nitrovinyl)phenoxy)-2-((4R,8R)-4,8,12-trimethyltridecyI)chroman (Scheme 7, 7e). Nitration was done by general procedure A with (R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)-6-(4-vinylphenoxy)chroman (0.2 mmol, 110 mg) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (0.5:99.5 v/v); bright yellowish solid; isolated yield: 90% (100 mg). 1H NMR (400 MHz, Chloroform-d) 5 0.76 - 0.99 (m, 14H), 0.99 - 1.20 (m, 3H), 1.20 - 1.48 (m, 11H), 1.48 - 1.74 (m, 3H), 1.74 - 1.92 (m, 2H), 1.92 - 2.06 (d, J = 14.6 Hz, 7H), 2.06 - 2.17 (s, 3H), 2.56 - 2.69 (t, J = 6.9, 6.9 Hz, 2H), 6.79 - 6.86 (d, J= 8.8 Hz, 2H), 7.42 - 7.49 (d, J= 8.7 Hz, 2H), 7.49 - 7.55 (d, J= 13.6 Hz, 1H), 7.93 - 8.02 (d, J= 13.6 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 12.04, 12.15, 13.02, 19.82, 19.88, 19.95, 20.81, 21.22, 22.83, 22.92, 24.04, 24.64, 25.01, 28.17, 31.32, 31.37, 32.85, 32.99, 37.48, 37.53, 37.58, 37.65, 37.74, 39.55, 40.16, 115.99, 118.27, 123.06, 123.78, 126.00, 127.84, 131.51, 135.20, 139.22, 142.95, 149.35, 162.56. HRMS (ESI): calcd. for C37H56NO4: 578.4209, found: 578.4196.


(E)-l-(chloromethyl)-4-(2-nitrovinyl)benzene (Scheme 8, 8b). Nitration was done by General Procedure C with l-(chloromethyl)-4-vinylbenzene (0.5 mmol, 70 μE, d=l taken) as the
(E)-4-(2-nitrovinyI)benzaldehyde (Scheme 8, 8a). Nitration was done by general procedure A with 1 -(chloromethyl)-4-vinylbenzene (0.5 mmol, 70 μL, d=l taken) as the substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); dark golden yellow solid; isolated yield: 82% (76 mg). lH NMR (400 MHz, Chloroform-d) δ 7.61 - 7.69 (d, J= 13.7 Hz, 1H), 7.69 -7.79 (m, 2H), 7.93 - 8.00 (m, 2H), 8.00 - 8.09 (d, J= 13.7 Hz, 1H), 9.79 - 10.42 (s, 1H). 13C NMR (101 MHz, Chloroform-d) δ 129.78, 130.09, 130.60, 133.11, 135.75, 137.47, 138.50, 139.32, 191.27. GC-MS (m/z): 177.1 [M]+. m. p. 108-109 °C.

substrate. Pure nitrated product was isolated by column chromatography through a silica gel column (mesh 100-200). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); yellow solid; isolated yield: 65% (70 mg). 1H NMR (400 MHz, Chloroform-d) δ 4.40 - 4.82 (s, 2H), 7.45 - 7.51 (in, 2H), 7.51 - 7.62 (m, 3H), 7.96 - 8.03 (d, 7= 13.7 Hz, 1H). 13C NMR (101 MHz, CDC13) δ 45.48, 76.91, 77.23, 77.55, 129.66, 129.70, 130.24, 137.66, 138.44, 141.71. GC-MS (m/z): 197.1 [M]+. m.p. 121-122 °C.
Characteristic data of starting materials prepared:

l,3,5-trimethyl-2-vinylbenzene. Reaction was done following General Procedure C with 2,4,6-trimethylbenzaldehyde (2 mmol, 294 μL) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; colorless liquid; isolated yield: 62% (180 mg). 1H NMR (400 MHz, Chloroform-d) δ 2.25 -2.44 (d, 7= 4.0 Hz, 9H), 5.25 - 5.35 (dd, 7= 18.0, 2.1 Hz, 1H), 5.52 - 5.60 (dd, 7 = 11.5, 2.1 Hz, 1H), 6.66 - 6.79 (dd, J= 17.9, 11.5 Hz, 1H), 6.90 - 6.95 (d, 7 = 1.0 Hz, 2H). 13CNMR(101 MHz, Chloroform-d) δ 21.01, 21.13, 119.24, 128.71, 134.98, 135.20, 135.88, 136.34.


1,2-divinylbenzene. Reaction was done following General Procedure C with phthalaldehyde (2 mmol, 268 mg) as the substrate. Pure olefin product was isolated by column chromatography
5-nitro-6-vinyIbenzo[d][l,3]dioxole. Reaction was done following General Procedure C with 6-nitrobenzo[d][l,3]dioxole-5-carbaldehyde (2 mmol, 390 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate / petroleum ether (3:97 v/v); yellow solid. 1H NMR (400 MHz, Chloroform-d) 5 5.41-5.44 (dd, 7=10.0, 4 Hz, 1H), 5.60-5.65 (dd, 7=10.0, 4.0 Hz, 1H),6.12 (s, 2H), 6.98 (s, 1H) 7.16-7.27 (m, 1H) 7.48 (s,lH). 13C NMR (101 MHz, Chloroform-d) 5 103.15, 105.38, 107.30, 118.07, 130.97, 133.35, 142.07, 147.63, 152.09.

through a silica gel column (mesh 60-120). Eluent: petroleum ether; colorless liquid. 1H NMR (400 MHz, Chloroform-d) δ 5.32 - 5.44 (dd, J= 11.0, 1.4 Hz, 2H), 5.61 - 5.76 (dd, J= 17.4, 1.4 Hz, 2H), 6.98 - 7.16 (dd, 7 = 17.4, 10.9 Hz, 2H), 7.27 - 7.36 (m, 2H), 7.45 - 7.57 (dd, J= 5.7, 3.5 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 116.53, 126.44, 127.99, 134.99, 136.23.

but-3-enylbenzene. Reaction was done following General Procedure C with 3-phenylpropanal (2 rnmol, 300 uL) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; yellow liquid; isolated yield: 50% (150 mg). 1H NMR (400 MHz, Chloroform-d) 5 2.38 (m, 2H), 2.72 (m, 2H), 5.00 (m, 2H), 5.80-5.90(m,lH), 7.15-7.20 (m, 3H), 7.21-7.30 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 5 35.59, 35.74, 115.11, 126.00, 128.49, 128.63, 138.30, 142.06.

(15,4R)-l-isopropyl-4-methyl-2-methylenecyclohexane. Reaction was done following General Procedure C with (25,,5R)-2-isopropyl-5-methylcyclohexanone (5 mmol, 860 μL) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; colorless liquid. 1H NMR (400 MHz, Chloroform-d) δ 0.87 - 0.90 (s, 1H), 0.90 - 0.92 (d, J= 1.7 Hz, 3H), 0.92 - 0.94 (d,J= 1.7 Hz, 3H), 0.94 - 0.97 (s, 2H), 1.02 - 1.44 (m, 2H), 1.47 - 1.63 (m, 1H), 1.63 - 1.74 (m, 2H), 1.74 -1.88 (m,2H), 1.88-2.15 (dq,J = 13.3, 6.6, 6.6, 6.6 Hz, 1H), 2.16-2.45 (m, 1H), 4.53-4.66 (d, J= 1.9 Hz, 1H), 4.66 - 4.87 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 19.23, 21.62, 22.34, 27.31, 27.61, 33.64, 34.24, 44.66, 49.62, 106.36, 151.28.

(3-methylbut-3-en-l-ynyl)benzene. Reaction was done following General Procedure C with 4-phenylbut-3-yn-2-one (2 mmol, 280 u.L) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether. H

NMR (400 MHz, Chloroform-d) 5 1.72 - 2.41 (m, 3H), 5.29 - 5.34 (m, 1H), 5.39 - 5.44 (dd, J = 2.1, 1.0 Hz, 1H), 7.28 - 7.38 (dd, J = 5.1, 2.0 Hz, 3H), 7.42 - 7.50 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 23.71, 76.91, 77.23, 77.54, 88.57, 90.75, 122.15, 123.44, 127.04, 128.33, 128.46,131.76.

(E)-buta-l,3-dieny]benzene. Reaction was done following General Procedure C with trans-cinnamaldehyde (4 mmol, 520 μL) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether. 1H NMR (400 MHz, Chloroform-d) δ 5.18 (m, 1H), 5.30-5.40 (m, 1H), 6.50-6.60 (m, 2H), 6.78-6.89(m, 1H), 7.20 (m, 1H), 7.31-7.40 (m, 2H), 7.40-7.50 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 117.84, 126.63, 127.83, 128.80, 129.80, 133.04, 137.30, 137.37.

buta-l,3-diene-l,l-diyldibenzene. Reaction was done following General Procedure C with 3,3-diphenylacrylaldehyde (1 mmol, 208 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; Colorless dense liquid. 1H NMR (400 MHz, Chloroform-d) δ 5.14 - 5.21 (m, 1H), 5.39 - 5.50 (m, 1H), 6.42-6.58(dddd,J= 16.9, 11.1, 10.1, 1.0 Hz, 1H), 6.71 - 6.82 (d, J= 11.0 Hz, 1H), 7.20 - 7.39 (m, 6H), 7.37 - 7.49 (m, 3H). 13C NMR (101 MHz, Chloroform-d) 5 118.81, 127.58, 127.69, 127.77, 128.35,128.38, 128.70, 130.60, 135.14, 139.82, 142.26, 143.31.


3-methyl-l-phenyl-4-vinyl-lH-pyrazole. Reaction was done following General Procedure C with 3-methyl-l-phenyl-lH-pyrazole-4-carbaldehyde (2 mmol, 372 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/petroleum ether (10:90 v/v); yellowish liquid; isolated yield: 81% (300 mg). 1H NMR (400 MHz, Chloroform-d)δ 2.35 - 2.46 (d, J = 0.5 Hz, 3H), 5.08 - 5.25 (dd, 7= 11.2, 1.4 Hz, IH), 5.42-5.55 (dd,J= 17.8, 1.4 Hz, 1H), 6.50-6.64 (ddd, J= 17.7, 11.2, 0.7 Hz, IH), 7.18-7.29(m, IH), 7.34 -7.48 (m, 2H), 7.54 -7.74 (m, 2H), 7.82 -7.97 (s, IH). 13CNMR(101 MHz, Chloroform-d) 8 12.96, 113.03, 118.72, 120.67, 124.56, 126.09, 126.76, 129.43, 139.92, 148.74.

5-phenyl-3-vinylisoxazoIe. Reaction was done following General Procedure C with 5-phenylisoxazole-3-carbaldehyde (1.5 mmol, 259 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; creamy solid; isolated yield: 43% (110 mg). 1H NMR (400 MHz, Chloroform-d) 8 5.46 - 5.79 (dd, J= 11.0, 0.9 Hz, IH), 5.79 - 6.20 (dd, J= 17.8, 0.9 Hz, 1H), 6.56 - 6.72 (s, IH), 6.72 - 6.93 (dd, J = 17.8, 11.0 Hz, IH), 7.33 - 7.56 (m, 3H), 7.69 - 7.87 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 8 96.32, 121.65, 125.39, 125.88, 127.41, 129.07, 130.30, 162.45, 169.87.

3-vinylbenzo{b]thiophene. Reaction was done following General Procedure C with benzo[b]thiophene-3-carbaldehyde (1.5 mmol, 243 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; yellowish liquid; isolated yield: 62% (150 mg). 1H NMR (400 MHz, Chloroform-d) δ 5.34 - 5.50 (dd, J= 11.1, 1.3 Hz, 1H), 5.75 - 5.93 (dd, J= 17.6, 1.3 Hz, 1H), 6.93 -7.10 (ddd, J= 17.6, 11.1, 0.8 Hz, IH), 7.32-7.59 (m, 3H), 7.81 -8.08 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 5 115.75, 122.11, 122.44, 123.04, 124.44, 124.62, 129.37, 134.70, 137.79, 140.63.


4-vinyldibenzo[b,d]furan. Reaction was done following General Procedure C with dibenzo[b,d]furan-4-carbaldehyde (1.4 mmol, 273 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; colorless liquid. 1H NMR (400 MHz, Chloroform-d) δ 5.50 - 5.69 (dt, J = 11.2, 1.1, 1.1 Hz, 1H), 6.19-6.44 (dt, J = 17.8, 1.1, 1.1 Hz, 1H), 7.06 - 7.21 (m, 1H), 7.29-7.43 (m, 2H), 7.43 - 7.58 (m, 2H), 7.58 - 7.73 (dq, J- 8.3, 0.7, 0.7, 0.7 Hz, 1H), 7.81 - 7.91 (dd, J = 7.7, 1.2 Hz, 1H), 7.91 - 8.06 (ddd, J= 7.7, 1.4, 0.7 Hz, 1H). I3C NMR (101 MHz, Chloroform-d) δ 111.96, 117.64, 119.95, 120.86, 122.77, 122.98, 123.01, 124.22, 124.79, 125.51, 127.36, 131.50, 153.89, 156.32.

2-bromo-5-vinylthiophene. Reaction was done following General Procedure C with 5-bromothiophene-2-carbaldehyde (0.26 mmol, 50 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; yellowish liquid; isolated yield: 83% (40 mg). 1H NMR (400 MHz, Chloroform-d) δ 5.09 - 5.20 (m, 1H), 5.41 - 5.54 (m, 1H), 6.63 - 6.78 (m, 2H), 6.85 - 6.99 (d, J = 3.8 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 111.43, 113.95, 126.25, 129.57, 130.36, 144.82.

(R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)-6-(4-vinylphenoxy)chroman.
Reaction was done following General Procedure C with 4-((R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yloxy)benzaldehyde (0.75 mmol, 400 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; colorless liquid; isolated yield: 53% (210 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.74 - 0.98 (dd, J= 7.9, 6.5 Hz, 15H), 0.98 - 1.18 (dddd, J= 24.9, 12.1, 7.1,3.4 Hz, 3H), 1.18 - 1.36 (m,9H), 1.36 - 1.57 (m, 3H), 1.58-1.71 (s, 3H), 1.71-1.91 (m, 2H), 1.92 - 2.07 (d, J= 16.2 Hz, 6H), 2.07 - 2.21 (s, 3H), 2.52 - 2.70 (t,J= 6.8, 6.8 Hz, 2H),

4.99 - 5.25 (dd, J= 10.8, 1.0 Hz, 1H), 5.51 - 5.70 (dd, J= 17.6, 1.0 Hz, 1H), 6.59 - 6.67 (m, 1H), 6.67 - 6.74 (d, J = 8.7 Hz, 2H), 7.27 - 7.32 (d, J = 8.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 12.03, 12.20, 13.07, 14.41, 19.83, 19.90, 19.97, 20.83, 21.25, 22.85, 22.94, 24.07, 24.66, 25.03, 28.20, 31.49, 32.89, 33.01, 37.50, 37.57, 37.61, 37.68, 37.78, 39.58, 40.17, 53.62, 60.60, 75.22, 111.72, 114.92, 118.06, 123.46, 126.42, 127.64, 128.34, 130.79, 136.43, 143.51, 148.93, 158.86.

(8R,9S,l0S,,13R,14S,17R)-10,13-dimethyl-3-inethylene-17-((R)-6-methylheptan-2-yl)hexadecahydro-lH-cyclopenta[a]phenanthrene. Reaction was done following General Procedure C with cholestan-3-one (1 mmol, 386 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; crystalline white solid; isolated yield: 55% (210 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.57 - 0.74 (s, 5H), 0.74-0.93 (m, 14H), 0.93 - 1.20 (m, 10H), 1.20 - 1.43 (m, 5H), 1.43 - 1.61 (m, 3H), 1.61 - 1.72 (dtd, J= 12.8, 3.9, 3.8, 2.7 Hz, 2H), 1.72 - 1.92 (m, 3H), 1.92 - 2.08 (m, 2H), 2.08 - 2.25 (m, 2H), 4.22 - 4.87 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 12.00, 12.30, 18.89, 21.35, 22.80, 23.06, 24.05, 24.44, 28.24, 28.48, 29.13, 31.25, 32.22, 35.69, 36.03, 36.19, 36.39, 38.18, 39.74, 40.06, 40.27, 42.80, 48.29, 54.58, 56.47, 56.70, 106.16, 150.41. HRMS (ESI): calcd. for C28H48: 407.3654, found: 407.3651.

(85,9S,10R,13S14S,17R)-10,13-dimethyl-17-(prop-l-en-2-yl)
2,3,4,7,8,9,10,ll,12,13,14,15,16,17-tetradecahydro-lH-cyclopenta[a]phenanthren-3-yl acetate. Reaction was done following General Procedure C with pregnenolone acetate (0.5 mmol, 179 mg) as the substrate. Pure olefin product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: petroleum ether; crystalline white solid; 1H NMR (400 MHz, Chloroform-d) δ 0.50 - 0.63 (s, 3H), 0.91 - 1.04 (s, 4H), 1.04 - 1.32 (m, 4H), 1.32 - 1.50 (m,2H), 1.50-1.61 (m, 2H), 1.61 -1.80(m, 5H), 1.80 - 1.93 (m, 3H), 1.93-2.13

(s, 4H), 2.24 - 2.39 (m, 2H), 4.52 - 4.67 (dddd, J = 14.6, 11.3, 5.6, 4.0 Hz, 1H), 4.67 - 4.76 (dt, J = 2.0, 1.0, 1.0 Hz, 1H), 4.80 - 4.89 (ddd, J= 2.3, 1.4, 0.8 Hz, 1H), 5.31 - 5.44 (dq, J= 4.7, 1.8, 1.5, 1.5 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 12.87, 19.53, 21.26, 21.63, 24.43, 24.85, 25.59, 27.95, 31.99, 32.37, 36.82, 37.20, 38.30, 38.81, 43.27, 50.36, 56.61, 57.40, 74.12, 110.90, 122.73, 139.86, 145.77, 170.70.

(8A,95,10R,13S,14S',17S)-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,ll,12,13,14,15,16,17-tetradecahydro-lH-cyclopenta[a]phenanthren-17-y! 4-vinylbenzoate. 4-vinylbenzoic acid (1 mmol, 148 mg), testosterone (1 mmol, 288 mg), DCC (1.2 mmol, 247 mg), DMAP (1.2 mmol, 146 mg) and DCM (10 mL) were taken in a round bottom flask and stirred at room temperature for overnight. The crude reaction mixture was purified through column chromatography (100-200 mesh); Eluent: ethyl acetate/petroleum ether (15:85 v/v); white solid; isolated yield 38% (160 mg). 1H NMR (400 MHz, Chloroform-d) δ 0.90 - 1.33 (m, 10H), 1.34 - 1.50 (m, 2H), 1.51-1.78 (m, 5H), 1.78- 1.95 (m, 3H), 1.95-2.17 (ddd, J= 13.4, 5.0, 3.2 Hz, 1H), 2.17-2.54 (m, 4H), 4.76 - 4.91 (dd, J = 9.1, 7.6 Hz, 1H), 5.30 - 5.45 (d, J= 11.0 Hz, 1H), 5.69 - 5.78 (m, 1H), 5.79 - 5.92 (d,J= 17.6 Hz, 1H), 6.63 - 6.85 (dd, J = 17.6, 10.9 Hz, 1H), 7.35 - 7.58 (m, 2H), 7.84 - 8.11 (m, 2H). 13C NMR (101 MHz, Chloroform-d) 8 12.46, 17.57, 20.71, 23.78, 27.84, 31.66, 32.92, 34.09, 35.59, 35.85, 36.89, 38.78, 43.05, 50.44, 53.86, 83.10, 116.62, 124.11, 126.25, 129.89, 129.98, 136.17, 142.01, 166.40, 171.18, 199.68.

(5R)-2-methyl-5-(prop-l-en-2-yI)cyclohex-2-enyl 4-vinylbenzoate. 4-vinylbenzoic acid (1 mmol, 148 mg), Z-carveol (1 mmol, 152 μL), DCC (1.2 mmol, 247 mg), DMAP (1.2 mmol, 146 mg) and DCM (10 mL) were taken in a round bottom flask and stirred at room temperature for overnight. The crude reaction mixture was purified through column chromatography (60-120 mesh); Eluent: ethyl acetate/petroleum ether (1:99 v/v); 1H NMR (400 MHz, Chloroform-d) 8

1.61 - 1.82 (m, 7H), 1.85 - 2.20 (m, 2H), 2.20 - 2.55 (m, 2H), 4.66 - 4.81 (m, 1H), 5.33 - 5.45 (dt, J= 10.9, 1.0, 1.0 Hz, 1H), 5.44 - 5.57 (dt, J= 3.8, 1.6, 1.6 Hz, 1H), 5.61 - 5.75 (m, 1H), 5.76-5.82 (dt, J =5.5, 1.9, 1.9 Hz, 1H), 5.82-5.91 (ddd, J= 17.6, 1.8, 0.8 Hz, 1H), 6.61 -6.89 (dd, J= 17.6, 10.9 Hz, 1H), 7.12 - 7.34 (s, OH), 7.34 - 7.60 (dd, J= 8.4, 1.4 Hz, 2H), 7.90 - 8.17 (m,2H).

N-(3-vinylphenyl)tetradecanamide. tetradecanoic acid (Myristic acid) ( 1 mmol, 228 uL) was taken in round bottom flask, 5 mL DMF was added to it and was stirred at 0 °C. HOBt (1.1 mmol, 140 mg), EDC (1.1 mmol, 160 mg) was added to it and stirred at 0 °C for 15 mins and then for 30 mins at room temperature. 3-vinylaniline (1 mmol, 113 μL) was added to it and reaction mixture was stirred at room temperature for overnight. The mixture was diluted with brine solution and extracted with ethyl acetate. Organic part was dried over Na2SO4 and concentrated at reduced pressure and product was purified through a silica gel column (mesh 60-120). White Solid; 1H NMR (400 MHz, Chloroform-d) δ 0.84 - 0.91 (d, J= 6.7 Hz, 3H), 1.19 - 1.27 (s, 18H), 1.52 - 1.65 (m, 1H), 1.65 - 1.79 (p, J= 7.6, 7.6, 7.5, 7.5 Hz, 2H), 2.10-2.59 (td, J= 7.6, 7.6, 3.7 Hz, 3H), 5.06 - 5.38 (d, J= 11.0 Hz, 1H), 5.63 - 5.86 (dd, J= 17.5, 0.9 Hz, 1H), 6.49 - 6.81 (dd, J = 17.6, 10.9 Hz, 1H), 7.09 - 7.18 (dt, J= 7.7, 1.3, 1.3 Hz, 1H), 7.18 -7.25 (m, 2H), 7.31 - 7.42 (m, 1H), 7.54 - 7.65 (t, J= 1.9, 1.9 Hz, 1H). I3C NMR (101 MHz, Chloroform-d) δ 14.33, 22.90, 24.94, 25.84, 29.29, 29.48, 29.57, 29.65, 29.70, 29.89, 32.13, 34.12,38.07, 114.64, 117.72, 119.36, 122.31, 129.29, 136.67, 138.41, 138.67, 171.80.
Competition experiment 1: Olefins are nitrated selectively or preferentially based on slight difference in steric and electronic environment



For entries 1-3, results are based on 1HNMR analysis of the crude reaction mixture.
For entries 4-6, results are based on TLC and GC-MS analysis of the crude reaction mixture.
Compatibility with both nitrogen and air: All the reactions were performed during monsoon; to prevent moisture nitrogen atmosphere was used. Later competition experiment under air and nitrogen reveled that this protocol is compatible with both air and nitrogen.


We claim,
1. A process for synthesizing a nitroolefin comprising nitrating an olefin with a nitrating agent selected from silver nitrite or ferric nitrate or tert-butyl nitrite and an oxylradical, TEMPO in the presence of dichloroethane as a solvent under conditions effective to yield the corresponding nitroolefin.
2. The process as claimed in claim 1, wherein the nitration occurs at a temperature of about 70°C.
3. The process as claimed in claim 1, wherein the nitration occurs efficiently an aerobic condition or under a nitrogen atmosphere.
4. The process as claimed in claim 1, wherein the olefin is selected from a group comprising styrene derivatives, aliphatic olefins, heterocyclic olefins, aromatic olefins, terminal and non-terminal aliphatic alkenes.
5. The process as claimed in claim 1, wherein the nitrated product is isolated by column chromatography through a silica gel column with a suitable eluent.
6. The process as claimed in claim 5, wherein the eluent is PET-ether / ethyl acetate.
7. The process as claimed in claims 1-6, wherein the yield of the nitrated olefin product is at least 60%.
8. A nitroolefin product obtained from a method according to any of the claims 1-7.