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
"A process for the synthesis of a-Trifluoromethyl Ketones by trifruoromethylation of olefins"
APPLICANT
Indian Institute of Technology, Bombay Powai, Mumbai 400076, Maharashtra, India; Indian
INVENTORS
Prof. Debabrata Maiti, Srimanta Manna, Arghya Deb, Atanu Modak and Soham Maity all Indian Nationals Of Indian Institute of Technology, Bombay, Department of Chemistry, Powai, Mumbai-400076, Maharastra, India; Indian
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 generally to a process for the synthesis of a-Trifluoromethyl Ketones. The present invention more particularly relates to a process for the synthesis of α-Trifluoromethyl Ketones by trifluoromethylation of olefins.
BACKGROUND OF THE INVENTION
Incorporation of -CF3 group in a molecule can have profound impact on its certain physiological properties. Due to the large hydrophobic domain and electron withdrawing property of -CF3 group, elevated lipophilicty, enhanced binding selectivity and increased metabolic stability can be conferred to a compound of pharmacological significance. In a current study, it was estimated that nearly 20% of existing drugs and 30% of agrochemicals contain fluorine [C.Isanbor, D.O'Hagan, J. Fluorine Chem. 2006,127, 303-319; J.P. Begue, D. Bonnet-Delpon, J. Fluorine Chem. 2006, 127, 992-1012]. Recently, a number of methods have emerged in literature that successfully installed the -CF3 functionality into commonly used motifs: aldehydes, ketones, esters, olefins etc.[D.A. Nagib, M. E. Scott, D. W. C, MacMillan, J. Am. Chem. Soc. 2009, 131, 10875 - 10876; P. V. Pham, D. A. Nagib, D. W. C. MacMillan, Angew. Chem. Int. Ed. 2011, 50, 9232-9232; A. T. Parsons, S. L. Buchwald, Angew. Chem. Int. Ed.
2011, 50, 9120-9123; A. T. Parsons, T. D. Senecal, S. I. Buchwald, Angew. Chem. Int. Ed.
2012, 51, 2947 -2950]. Of those, synthesis of α-Trifluromethyl carbonyls has been of fundamental interest from synthetic point of view.
Generally, a-Trifluromethyl carbonyls are synthesized from the silyl enol ethers and
enolates by means of various radical and electrophilic trifluoromethylating agents [K. Sato, T.
Yuki, R. Yamaguchi, T. Hamano, A. Tarui, M. Omote, I Kumadaki, A. Ando, J. Org. Chem.
2009, 74, 3815-3819; I. Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007, 46,

754-757; Y. Itoh, K. Mikami, Org. Lett. 2005, 7, 649-651; dY. Itoh, K. Mikami, Org. Lett. 2005, 7, 4883-4885]. To synthesize these precursors often strong base such as LDA has to be employed, thus limiting the methods by extra synthetic steps, precautionary measures. Prodution of α-Trifluroethyl carbonyls in excellent enantioselectivity from the corresponding aldehydes, ketones, esters etc. by using a photoredox organocatalysis in a single step is reported [ P. V. Pham, D. A. Nagib. D. W. C. MacMillan, Angew. Chem. Int. Ed. 2011, 50, 9232-9232;] Very recently in 2012, a nucleophilic trifluoromethylation of α-halo ketones was reported with fluoroform derivedCuCF3 reagent that circumvented the problem of 1,2-addition of CF3 group across the C=0 bond (Scheme 1) [P. Novak, A. Lishchynskyi, V. V. Grushin, J. Am. Chem. Soc. 2012, 134, 16167-16170; A. Zanardi, U.A. Novikov, E. Martin, J. Benet, Buchholz, V. V. Grushin, J. Am. Chem. Soc.2011, 133, 20901-20913]. These approaches have contributed significantly to construct synthetically useful α-Trifluromethyl carbonyl scaffolds, though the use of expensive reagents and catalysts, limited functional group tolerance, requirement of cryogenic temperature and prefunctionalized substrates call for development of more practical and economic methods to synthesize α-Trifluromethyl carbonyls.
On this backdrop, it is desirable to produce cost effective a-Trifluromethyl ketones in excellent yields, which is prepared by the process developed by the inventor of the present invention with rather inexpensive Lingoes reagent as the trifluoromethylation agent (Scheme 2).
Scheme 1. Different approaches to synthesize α-Trifluromethyl ketenes


SUMMARY OF THE INVENTION
In accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention provides a process for trifluoromethylation of simple unactivated olefins for the synthesis of a-Trifluoromethyl Ketones.
Widely available olefins feed stock can be used as starting material. While inexpensive Langlois reagent is used as trifluoromethylation agent.
Scheme 2. Trifluoromethylation of unactivated olefins: Synthesis of α-Trifluromethyl ketones


A major advantage of this process of synthesis is its cost effectiveness. The reaction is also carried out at room temperature and under atmospheric condition. Almost quantitative yields of α-trifluoromethyl ketones are obtained by this simple and cost effective process.
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 and 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.
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 the invention pertains.

The present invention pertains to a process for the synthesis of α-Trifluoromethyl Ketones by trifluoromethylation of olefins.
As used herein, Dimethylformamide is an organic compound with the formula (CH3)2NC(0)H. Commonly abbreviated as DMF (though this acronym is sometimes used for dimethylfuran), this colourless liquid is miscible with water and the majority of organic liquids. DMF is a common solvent for chemical reactions. Dimethylformamide is a polar (hydrophilic) aprotic solvent with a high boiling point.
Experimentation has made it clear that Dimethylformamide (DMF) is the best solvent and the catalyst used is sodium triflinate which is commonly known as Langlois reagent. It is noted that greater amount of DMF was required to achieve satisfactory conversion. Optimized reaction conditions required only 2 equivalents of triflinate and 0.2 equivalents of AgNO3/K2S2O3 and reaction could also be carried out in open flasks at room temperature.
Reaction Scheme with styrenes is shown herein below: Scheme 3. Scope of the reaction with styrenes

Styrene itself gave the desired product in an excellent 92% yield. Substituents bearing different steric and electronic properties at various positions did no harm to the efficacy of the reaction. A wide variety of functional groups ranging from -NO2, -CN, -CHO, -CCO2Me to -Me, -OMe were tolerated owing to the exceptionally mild reaction condition and corresponding a-Trifluromethyl ketones were obtained in 56-92% isolated yields (Scheme 3, entries 3b,3c and 3f-3p). Different halogen substituents (X= F, C1, Br) on styrene were tolerated as well (Scheme 3, entries 3f-3h). Vinyl naphthalene exhibited even superior reactivity as naphthalenes containing vinyl group at 1- and 2- positions yielded the desired product in 89% and 95% isolated yields respectively (Scheme 3, entries 3d and 3e). It is noted that incorporation of -CF3 group was observed exclusively on styrene double bond due to greater stability of the benzylic radical (Scheme 3, entry 3j).
Scope of the reaction with internal olefins is given hereunder in Scheme 4: Scheme 4. Scope of the reaction with internal olefins

Indene and 1, 2-dihydronaphthalene were reacted successfully to generate five- and six-membered cyclic ketones respectively, containing trifluoromethyl functionality at α- position (Scheme 4, entries 4b and 4c). Notably, di-substituted olefins are more challenging as substituents at both ends of the double bond increase steric demand. On the other hand, ubiquitous presence of such olefins insists synthetic methods to be compatible with them. Both

cis- and trans- stilbenes (4d) reacted successfully in the present reaction condition. Styrene with methyl group at the β- position reacted as efficiently as the unsubstituted styrene itself (Scheme 4, entry 4a).
Scope of the reaction with heteroaromatic olefins is given hereunder in Scheme 5: Scheme 5. Scope of the reaction with heteroaromatic olefins and aliphatic olefins

CF3 group was successfully incorporated onto vinyl group at 3-position of benzothiophene with an excellent 86% isolated yield (5a). One and two N atoms containing indole and pyrazole based olefins reacted as well (Scheme 5, entries 5b, 5d ). As used herein, the term an alkene, olefin, or define is an unsaturated chemical compound containing at least one carbon-to-carbon double bond. The simplest acyclic alkenes, with only one double bond and no other functional groups, form a homologous series of hydrocarbons with the general formula CnH2n.
From the description herein before it is clear that the olefins could be substituted olefins, olefins containing aromatic or heteroartomatic rings having substituents like lower alkyl, halogens, alkoxide, cyano, nitro and aldyhyde groups.

This synthesis is carried out with unactivated olefins and not radio labeled a-Trifluoromethyl Ketones.
Compounds containing α-Trifluromethyl keto- group can be utilized as useful synthetic precursors for production of various molecules of commercial importance. Recently, several methods have included -CF3 group selectively at 3-position of indole while using expensive trifluoromethylation agents. Using the present method such scaffold can easily be accessed with another additional step starting from simple unactivated olefin. Acidity of α- position of ketones can significantly be increased due to the strong electron withdrawing property of CF3 group; facile a- arylation can be performed by employing only a mild base. Addition of -CF3 and -OH groups across an olefin double bond is still to be realized in a single step. By following one pot-two step method, these synthetically challenging scaffolds can be prepared in an atom economical way. Scheme 6. Synthetic application of a-Trifluromethyl ketones

In conclusion, inventors have discovered a very efficient and economical method to access synthetically useful α-Trifluromethyl ketones. Simple unactivated olefins of aromatic and heteroaroamtic origin have been employed as the starting material. Wide functional group

tolerance, mild reaction condition and use of inexpensive reagents in every-day set up are some exciting features of this newly developed trifluoromethylation reaction.
Accordingly, this invention relates to a process for trifluoromethylation of olefins which comprises reacting olefins with sodium triflinate NaSO2CF3 (Langlois Reagent) in the catalytic presence of Ag / K2S2O8 in a solvent medium of DMF either alone or in admixture with water at ambient temperature in the presence of atmospheric oxygen and recovering α-Trifluoromethyl Ketone from the reaction mixture.
Experiments:
Reagent Information. Unless otherwise stated, all reactions were carried out under air atmosphere in screw cap reaction tubes. All the solvents were bought from Aldrich in sure-seal bottle and were used as received. Sodiumtriflinate was purchased from Aldrich. All the olefins were bought from Aldrich and alfa Aesar. For column chromatography, silica gel (60-120 mesh or 100-200 mesh) obtained from SRL Co. were used. A gradient elution using pet ether and ethyl acetate was performed, based on Merck aluminium TLC sheets (silica gel 6OF254).
Analytical Information. All isolated compound are characterized by 1H NMR,19F and l3C NMR spectroscopy and Gas chromatography mass spectra (GC-MS); Also HR-MS data of some compound are given. Copies of the 'H 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 lH 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 l3C NMR spectra were reported in ppm relative to deuterochloroform (77.23 ppm), unless otherwise stated, and all were obtained with ]H decoupling. All GC analyses were performed on a Agilent 7890A GC system with an FID detector using a J & W DB-1 column (10 m, 0.1 mm I.D.) using n-decane as the internal standard. All GCMS analysis was done by Agilent 7890A GC system connected with 5975C inert XL EI/CI MSD (with triple axis detector).


Fig. 1. 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].
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 compositions, 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.
EXAMPLES: (a-ag)
General Procedure for Trifluoromethylation of Olefins under air using DMF as the

solvent.
An oven-dried screw cap reaction tube was charged with a magnetic stir-bar, NaS02CF3 (0.5mmol, 78 mg), K2S208 (0.05 mmol, 13.5 mg) and AgN03 (0.05 mmol, 9 mg). Also depending on the physical state of the starting olefin, solid compounds were weighed along with the reagents and liquid olefin was added under air atmosphere and 4 mL DMF were added by micro-liter syringe and laboratory syringe respectively. The reaction tube was placed at room temperature and the reaction mixture was stirred vigorously for 24h. After 24 h, the reaction mixture was diluted with Et20 and filtered through a cefite pad. The celite pad was washed with Et2O Et2O (40 mL) and water (30 mL) were added at agitation in air. The organic layer was separated and the aqueous layer was washed with Et20 (3 x 20 mL). The combined filtrate was dried over Na2SO4. After filtration and evaporation of the solvent, the crude mixture was purified by column chromatography using silica gel (60-120/100-200 mesh size) and Petroleum-ether / ethyl acetate as the eluent.

a) 3,3,3-trifluoro-l-phenylpropan-l-one (Scheme3; entry 3a). Trifluoromethylation was done by general procedure A with styrene (0.25mmol, 29 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); white solid; isolated yield: 92% (47 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.76 - 3.85 (q, J = 10.0, 10.0, 10.0 Hz, 2H), 7.48 - 7.54 (m, 2H), 7.61 - 7.66 (m, 1H), 7.92 -7.96(m, 2H). I3CNMR(101 MHz, CDC13)δ 41.84, 42.12, 42.40, 42.68, 122.84, 128.54, 129.14, 134.42, 138.99, 189.95. 19F NMR (376 MHz, CDC13) δ -62.16, -62.13, -62.10. m.p. 41°C.

b) 3,3,3-trifluoro-l-p-tolylpropan-l-one (Scheme 3; entry 3b). Trifluoromethylation was done by general procedure A with 4-methyl-styrene (0.25mmol, 33 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); white solid; isolated yield:

85% (43 mg); lH NMR (400 MHz, Chloroform-d) δ 2.41 - 2.44 (s, 3H), 3.72 - 3.82 (q, J= 10.0, 10.0, 10.0 Hz, 2H), 7.28 - 7.33 (m, 2H), 7.80 - 7.91 (m, 2H). 13C NMR (101 MHz, CDC13)δ 21.90, 41.73, 42.01, 42.29, 42.56, 125.79, 128.68, 129.80, 133.56, 145.52, 189.55. 19F NMR (376 MHz, CDC13)δ -61.78, -61.75, -61.72. HRMS (ESI): calcd. for C10H10F3O: 203.0681, found: 203.0684. m.p. 56-60 °C.

c) 3,3,3-trifluoro-l-(4-methoxyphenyl)propan-l-one (Scheme 3; entry 3c),
Trifluoromethylation was done by general procedure A with 4-methoxy styrene (0.25 mmol, 35 μL) as the substrate and K2S208 (0.025mmol, 7 mg). Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); colourless liquid; isolated yield: 70% (38 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.68 - 3.79 (q, J= 10.1, 10.1, 10.1 Hz, 2H), 3.87 - 3.88 (s, 3H), 6.91 - 7.03 (m, 2H), 7.86 - 7.95 (m, 2H). 13C NMR (101 MHz, CDCI3) δ 41.60, 41.88, 42.16, 42.44,55.79, 114.29, 122.94, 129.11, 131.02, 164.54, 188.36. 19F NMR (376 MHz, CDCI3) δ -62.00,-61.97,-61.95.

d) 3,3,3-trifluoro-l-(4-fluorophenyI)propan-l-one (Scheme 3; entry 3d)
Trifluoromethylation was done by general procedure A with (0.25 mmol, 30.5 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:98 v/v); colourless liquid; isolated yield: 81% (42 mg).1H NMR (400 MHz, Chloroform-d)δ 3.70 - 3.83 (q, J = 9.9, 9.9, 9.9 Hz, 2H), 7.12 - 7.23 (m, 2H), 7.92 - 8.01 (m, 2H). 13C NMR (101 MHz, CDC13) δ 41.86, 42.14, 42.42, 42.71, 116.28, 116.50, 131.30, 131.40, 167.83, 188.36. 19F NMR (376 MHz, CDCl3) δ -102.91, -102.89, -102.88, -102.87, -102.86, -102.85, -102.83, -62.08, -62.05, -62.03.


e) l-(4-chlorophenyl)-3,3,3-trifluoropropan-l-one (Scheme 3; entry 3e).
Trifluoromethylation was done by general procedure A with l-chloro-4-vinylbenzene (0.25 mmol, 30 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:98 v/v); white solid; isolated yield: 83% (46 mg). 1H NMR (400 MHz, Chloroform-d) 8 3.39 - 3.91 (q, J = 9.9, 9.9, 9.9 Hz, 2H), 7.41 - 7.54 (m, 2H), 7.69 - 7.99 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 41.91, 42.20, 42.48, 42.76, 122.65, 129.52, 129.96, 134.27, 141.10, 188.75. 19F NMR (376 MHz, CDC13) δ -62.04, -62.01, -61.99. m.p. 55 °C.

f) l-(4-bromophenyl)-3,3,3-trifluoropropan-l-one (Scheme 3; entry 3f). Trifluoromethylation was done by general procedure A with l-bromo-4-vinylbenzene (0.25 mmol, 33 μL) as the substrate. Pure trifluoromethylated 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: 81% (54 mg). 1H NMR (400 MHz, Chloroform-d)δ 3.66 - 3.83 (ad, J= 9.9, 9.9, 9.9, 0.7 Hz, 2H), 7.61 - 7.70 (m, 2H), 7.78 - 7.83 (dt, J - 9.0, 2.2, 2.2 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 41.91, 42.19, 42.48, 42.76, 122.62, 125.37, 130.02, 132.53, 134.66, 188.98. 19F NMR (376 MHz, CDC13) δ -61.96. -61.94, -61.91. m.p. 75 °C

h) 3,3,3-trifluoro-l-(4-nitrophenyl)propan-l-one (Scheme 3; entry 3h). Trifluoromethylation was done by general procedure A with 4-nitrostyrene (0.25 mmol, 32μL) as the substrate. Pure
g) 4-(3,3,3-trifluoropropanoyl) benzonitrile (Scheme 3; entry 3g), Trifluoromethylation was done by general procedure A with 4-cyano styrene (0.25 mmol, 32μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); white solid; isolated yield: 72% (38.5 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.69 - 4.02 (q, J= 9.8, 9.8, 9.8 Hz, 2H), 7.80 - 7.86 (m, 2H), 8.01 - 8.06 (m, 2H). 13C NMR (101 MHz, CDC13) δ 42.21, 42.50, 42.79, 43.07, 117.71, 122.39, 125.15, 128.96, 132.99, 138.67, 188.74. 19F NMR (376 MHz, CDC13) δ -62.02, -62.00, -61.99. m.p. 138 °C.


trifluoromethylated 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: 83% (48.5 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.79 - 3.96 (q, J= 9.7, 9.7, 9.7 Hz, 2H), 8.08 - 8.14 (m, 2H), 8.32 - 8.42 (m, 2H). 13C NMR (101 MHz, CDC13) δ 42.48, 42.76, 43.05, 43.34, 122.36, 124.38, 125.12, 129.68, 140.12,151.11, 188.57. 19F NMR (376 MHz, CDC13) δ -62.01,-61.98,-61.95.

i) methyl 4-(3,3,3-trifluoropropanoyI)benzoate (Scheme 3; entry 3i). Trifluoromethylation was done by general procedure A with methyl 4-vinylbenzoate (0.25 mmol, 40.5 mg) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); white solid; isolated yield:72% (44 mg). 'H NMR (400 MHz, Chloroform-d) 5 3.79 - 3.88 (q, J= 9.8, 9.8, 9.8 Hz, 2H), 3.95 - 3.97 (s, 3H), 7.97 - 8.01 (m, 2H), 8.14 - 8.18 (m, 2H). 13C NMR (101 MHz, CDCl3) 8 42.21, 42.49, 42.78, 43.06, 52.84, 122.61, 128.48, 130.30, 135.06, 166.07, 189.50.19F NMR (376 MHz, CDC13) 8 -62.09, -62.06, -62.03. m.p. 73 °C.

j) 3,3,3-trifluoro-l-m-tolylpropan-l-one (Scheme 3; entry 3j). Trifluoromethylation was done by general procedure A with styrene (0.25mmol, 40 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:99 v/v); yellow liquid; isolated yield: 83% (42 mg). 1H NMR (400 MHz, Chloroform-d) δ 2.35 - 2.50 (m, 3H), 3.66 - 3.88 (q, J = 10.0, 10.0, 10.0 Hz, 2H), 7.32 - 7.49 (m, 2H), 7.63 - 7.80 (m, 2H). I3C NMR (101 MHz, CDC13) 5 21.49,41.85,42.13,42.40,42.68, 122.88, 125.78, 128.99, 135.18, 136.02, 139.07, 190.12. I9F NMR (376 MHz, CDCI3) δ -62.00, -61.97, -61.95.

k) 3-(3,3,3-trifluoropropanoyl)benzaldehydeone (Scheme 3; entry 3k). Trifluoromethylation was done by general procedure A with 3-vinylbenzaldehyde (0.25 mmol, 32 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); colorless liquid; isolated yield: 71% (38.34 mg). 1H NMR (400 MHz, Chloroform-d) 8 3.81 - 3.93 (q, J= 9.9,

9.9, 9.9 Hz, 2H), 7.68 - 7.76 (t, J = 7.7, 7.7 Hz, 1H), 8.12 - 8.18 (dt, J= 7.6, 1.4, 1.4 Hz, 1H), 8.19-8.25 (dt, .J=7.8, 1.6, 1.6 Hz, 1H), 8.38 - 8.44 (s, J= 1.8, 1.8 Hz, 1H), 10.07 - 10.13 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 42.09, 42.38, 42.66, 42.94, 122.58, 129.40, 130.15, 133.89, 135.00, 137.01, 188.97, 191.23. 19F NMR (376 MHz, CDCl3) δ -63.37, -63.40, -63.43. 'HRMS (ESI): calcd. for C10H8F3O2: 217.0468, found: 217.0467.

1) 3,3,3-trifluoro-l-(3-nitrophenyl)propan-l-one(Scheme 3; entry 31). Trifluoromethylation was done by general procedure with 3-nitro styrene (0.25 mmol, 38 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); yellow solid; isolated yield: 79% (46 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.83 - 3.94 (q, J = 9.7, 9.7, 9.7 Hz, 2H), 7.71-7.79 (t,J= 8.0, 8.0 Hz, 1H), 8.26- 8.31 (dt,J=7.8, 1.4, 1.4 Hz, 1H), 8.45 - 8.53 (ddd,y = 8.2, 2.3, 1.1 Hz, 1H), 8.71 - 8.78 (s, J= 2.0, 2.0 Hz, 1H). 13C NMR (101 MHz, CDC13) δ 42.23, 42.52, 42.81, 43.09, 123.41, 128.63, 130.59, 134.00, 137.06, 148.71, 188.01. 19F NMR (376 MHz, CDCl3) δ -62.00, -61.97, -61.95.

m) l-(4-(chloromethyl)phenyl)-3,3,3-trifluoropropan-l-one (Scheme 3; entry 3m).
Trifluoromethylation was done by general procedure A with l-(chloromethyl)-4-vinylbenzene (0.25 mmol, 36 μL) as the substrate and AgN03 (0.025mmol, 4.5 mg). Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); white solid; isolated yield: 76% (345 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.72 - 3.86 (q, J = 10.0, 10.0, 10.0 Hz, 2H), 4.56 - 4.68 (s, 2H), 7.50 - 7.59 (m, 2H), 7.89 - 8.00 (m, 2H). 13C NMR (101 MHz, CDC13) δ 41.96, 42.24, 42.52, 42.81, 45.23, 125.48, 129.03, 135.74, 143.83, 189.36. 19F NMR (376 MHz, CDC13) δ -62.03,-62.01,-61.98. m.p. 80 °C.

n) l-(2-chlorophenyl)-3,3,3-trifluoropropan-l-one(Scheme 3; entry 3n):
Trifluoromethylation was done by general procedure A with allyl l-chloro-2-vinylbenzene (0.25 mmol, 35 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); colorless liquid; isolated yield 80% (44.40 mg). lH NMR (400 MHz, Chloroform-d) 6 3.81 - 3.93 (q, J= 10.0, 10.0, 10.0 Hz, 2H), 7.35 - 7.42 (m, 1H), 7.43 - 7.50

(m, 2H), 7.53 -7.57 (dt,J= 7.7, 1.0, 1.0 Hz, 1H). 13CNMR(101 MHz, CDC13) δ 45.93, 46.21, 46.49, 46.77, 122.38, 125.14, 127.53, 129.93, 130.97, 131.42, 133.18, 189.78. 19F NMR (376 MHz, CDCl3) δ -62.23, -62.20, -62.18.

o) l-(2-bromophenyl)-3,3,3-trifluoropropan-l-one (Scheme 3; entry 3o):
Trifluoromethylation was done by general procedure A with allyl l-bromo-2-vinylbenzene (0.25 mmol, 46 μL) as the substrate. Pure trifluoromethyiated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); yellow liquid ; isolated yield 83% (55 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.79 - 3.90 (q, J= 9.9, 9.9, 9.9 Hz, 2H), 7.34 - 7.41 (m, 1H), 7.41 - 7.47 (m, 2H), 7.62 - 7.67 (m, 1H). I3C NMR (101 MHz, CDC13) δ 45.61, 45.89, 46.17, 46.46, 119.04, 122.29, 125.05, 127.99, 129.38, 132.92, 134.14, 193.49.19F NMR (376 MHz, CDCl3) δ-62.16,-62.13,-62.10.

p) 3,3,3-trifluoro-l-o-tolylpropan-l-one (Scheme 3; entry 3p): Trifluoromethylation was done by general procedure A with allyl l-methyl-2-vinylbenzene (0.25 mmol, 33 μL) as the substrate. Pure trifluoromethyiated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); colourless liquid; isolated yield 83% (42 mg). 1H NMR (400 MHz, Chloroform-d) 8 2.54 - 2.55 (s, 3H), 3.69 -3.82(q,J = 10.1, 10.1, 10.1 Hz, 2H), 7.28 -7.33 (t, J= 7.5, 7.5 Hz, 2H), 7.42 -7.47 (td, 7= 7.5, 7.4, 1.4Hz, 1H), 7.59 -7.64 (dd,J = 7.4, 1.7 Hz, 1H). 13C NMR (101 MHz, CDC13) δ 21.77, 44.19, 44.47, 44.74, 45.01, 126.14, 129.13, 132.72, 136.13, 139.81, 192.94. 19F NMR (376 MHz, Chloroform-d) δ -62.88, -62.86, -62.82.

q) 3,3,3-trifluoro-l-(naphthaIen-2-yl)propan-l-one (Scheme 3; entry 3q).
Trifluoromethylation was done by general procedure with 2-vinylnaphthalene (0.25 mmol, 38.5 mg) as the substrate. Pure trifluoromethyiated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:98 v/v); white solid; isolated yield: 95% (56.5 mg). 'H NMR (400 MHz, Chloroform-d)δ 3.88 - 4.00 (q, J= 10.0, 10.0, 10.0 Hz, 2H), 7.55-7.70 (dddd,7= 23.6, 8.1, 6.9, 1.3 Hz, 2H), 7.90-8.03 (m,

4H), 8.39 - 8.45 (m, 1H). 13C NMR (101 MHz, CDC13) 5 41.92, 42.20, 42.48, 42.76, 122.92, 123.64, 127.40, 128.06, 129.13, 129.41, 129.90, 130.75, 132.51, 136.15, 189.84.19F NMR (376 MHz, CDC13) δ -61.92, -61.89, -61.87. HRMS (ESI): calcd. for C13H10F3O: 239.0687, found: 239.0684. m.p. 83 °C.

r) 3,3,3-trifluoro-l-(naphthalen-l-yl)propan-l-one (Scheme 3; entry 3r).
Trifluoromethylation was done by general procedure with 1-Vinylnaphthalene (0.25mmol, 27 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent; ethyl acetate/ petroleum ether (2:98v/v); colourless liquid; isolated yield: 89% (53 mg). 1H NMR (400 MHz, Chloroform-d) 8 3.82 - 4.02 (q, J= 10.0, 10.0, 10.0 Hz, 2H), 7.51 - 7.56 (dd, J = 8.2, 7.3 Hz, IH), 7.55 - 7.60 (ddd, J= 8.2, 6.9, 1.3 Hz, 1H), 7.62 -7.67 (ddd, J =8.6, 6.9, 1.5 Hz, 1H), 7.82 - 7.97 (ddd, J= 11.9, 7.7, 1.5 Hz, 2H), 8.01-8.11 (dt, 7=8.3, 1.0, 1.0 Hz, IH), 8.68- 8.78 (dq, J= 8.6, 0.9, 0.9, 0.9 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 44.74, 45.01, 45.29, 45.57, 122.81, 124.37, 125.80, 127.14, 128.79, 128.96, 129.03, 130.38, 133.98, 134.22, 134.50, 193.05. 19F NMR (376 MHz, CDCl3) δ -61.91,-61.94,-61.96.

s) allyl 4-(3,3,3-trifluoropropanoyl)benzoate (Scheme 3; entry 3s): Trifluoromethylation was done by general procedure A with allyl 4-vinyIbenzoate(0.25 mmol, 47 mg) as the substrate.-Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); white solid; isolated yield 65% (46 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.79 - 3.88 (q, J=.8, 9.8, 9.8 Hz, 2H), 4.83-4.88 (dt,y= 5.8, 1.4, 1.4 Hz, 2H), 5.30 - 5.35 (dq, J- 10.4, 1.3, 1.3, 1.3 Hz, IH), 5.39 - 5.46 (dq, J =17.2, 1.5, 1.5, 1.5 Hz, IH), 5.99-6.10 (ddt,J = 17.1, 10.4,5.8,5.8 Hz, IH), 7.97 - 8.01 (m, 2H), 8.16 - 8.20 (m, 2H). 13C NMR (101 MHz, CDCl3) 5 42.22, 42.50, 42.78, 43.07, 66.40, 119.09, 122.60, 125.36, 128.48, 130.35, 133.90, 135.09, 139.00, 165.23, 189.49. 19F NMR (376 MHz, CDCl3) δ -62.07, -62.04, -62.02. HRMS (ESI): calcd. for C13H11,F3Na03: 295.0558, found: 295.0552. m.p. 83 °C.


t) prop-2-ynyl 4-(3,3,3-trifluoropropanoyl)benzoate (Scheme 3; entry 3t):
Trifluoromethylation was done by general procedure A prop-2-ynyl 4-vinylbenzoate (0.25 mmol, 46.5 mg) as the substrate. Pure trifluoromethyiated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); colourless liquid; isolated yield 73% (49 mg). 'H NMR (400 MHz, Chloroform-d) δ 2.53 - 2.56 (t, J= 2.4, 2.4 Hz, 1H), 3.79 - 3.88 (q, J= 9.9, 9.9, 9.9 Hz, 2H), 4.94 - 4.97 (m, 2H), 7.97 - 8.02 (m, 2H), 8.17 - 8.22 (m, 2H). 13C NMR (101 MHz, CDC13) δ 42.27, 42.55, 42.84, 43.12, 53.24, 75.71, 76.91, 122.59, 125.34, 128.53, 130.54, 134.31, 139.31, 164.81, 189.41. 19F NMR (376 MHz, CDCl3) δ -62.09, -62.06, -62.04. HRMS (ESI): calcd. for C13H9F3Na03: 293.0394, found: 293.0396.

u) (lS,5S)-4,6,6-trimethylbicyclo[3.1.1]hept-3-en-2-yl4-(3,3,3-trifluoropropanoyl)benzoate (Scheme 3; entry 3u). Trifluoromethylation was done by general procedure A with (15,55)-4,6,6-trimethylbicyclo [5.1.1]hept-3-en-2-yl 4-vinylbenzoate (0.25 mmol, 70.5 mg) as the substrate. Pure trifluoromethyiated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (10:90 v/v); colourless liquid; isolated yield: 75% (69 mg). 'H NMR (400 MHz, Chloroform-d) δ 1.12 - 1.17 (s, 3H), 1.36-1.41 (s,3H), 1.46-1.51 (d, J= 9.2 Hz, 1H), 1.76-1.81 (t,J=1.7, 1.7 Hz, 3H), 2.04-2.10 (m, 1H), 2.43 - 2.49 (tdd, J = 5.9, 5.9, 3.4, 1.8 Hz, 1H), 2.52 - 2.59 (ddd, J= 9.2, 6.3, 5.2 Hz, 1H), 3.79- 3.87 (q,J = 10.0, 9.9, 9.9 Hz, 2H), 5.39 - 5.46 (dh, 7= 3.3, 1.7, 1.7, 1.6, 1.6, 1.6 Hz, 1H), 5.77 -5.82 (tq, J =3.2, 3.2, 1.7, 1.7, 1.6 Hz, 1H), 7.95 - 8.01 (m, 2H), 8.11 - 8.16 (m, 2H). 13C NMR (101 MHz, CDC13) δ 22.96, 23.12, 26.85, 35.85, 40.02, 42.20, 42.48, 42.76, 43.05, 45.78, 47.81, 115.42, 122.63, 125.38, 128.45, 130.24, 135.94, 138.78, 150.69, 165.28, 189.55. 19F NMR (376 MHz, CDC13) δ -62.06, -62.04, -62.00. HRMS (ESI): calcd. for C20H21F3NaO3: 389.1334, found: 389.1335.


v) 3,3,3-trifluoro-l-(4-((3-phenyl-lH-pyrazol-l-yl)methyl)phenyl)propan-l-one (Scheme 3; entry 3v). Trifluoromethylation was done by general procedure A with 3-phenyl-l-(4-vinylbenzyl)-lH-pyrazole (0.25 mmol, 65 mg) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); yellowliquid; isolated yield: 72% (62 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.70 - 3.81 (m, 2H), 5.41 - 5.47 (s, 2H), 6.61 - 6.64 (d, J= 2.3 Hz, 1H), 7.24 - 7.36 (m, 3H), 7.36 - 7.45 (m, 3H), 7.79 - 7.84 (m, 2H), 7.85 - 7.92 (m, 2H). 13C NMR (101 MHz, CDC13) δ 41.92, 42.20, 42.48, 42.76, 55.64, 103.96, 125.85, 127.89, 128.86, 129.10, 131.28, 133.41, 135.50, 143.60, 152.41,189.37.19F NMR (376 MHz, CDC13) δ -62.02, -61.99, -61.97. HRMS (ESI): calcd. for C19H16F3N2O2: 345.1213, found: 345.1209.

w) (R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl-4-(3,3,3-
trifluoropropanoyl)benzoate (Scheme 3; entry 3w): Trifluoromethylation was done by general procedure A with (R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl 4-vinylbenzoate (0.2mmol, 112 mg) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); yellow white solid; isolated yield 50% (64.4 mg). 1H NMR (400 MHz, Chloroform-d) S 0.74-0.97 {t,J= 6.7, 6.7 Hz, 13H), 1.00-1.18 (m, 3H), 1.18-1.44 (m, 12H), 1.47-1.66 (dtd,J= 26.5, 13.2, 10.8, 6.1 Hz, 3H), 1.71 - 1.88 (td,J= 12.0, 10.4, 6.1 Hz, 2H), 1.98-2.21 (m, 10H), 2.58-2.72 (m, 3H), 3.81 - 3.94 (q, J= 9.8, 9.8, 9.8 Hz, 1H), 7.96 - 8.16 (m, 2H), 8.29 - 8.43 (m, 2H). 13C NMR (101 MHz, CDC13) δ 12.09, 12.44, 13.28, 19.82, 19.86, 19.88, 19.91, 19.97, 20.86, 21.26, 22.85, 22.94, 24.67, 25.05, 27.16, 28.20, 29.92, 33.00, 37.50, 37.61, 37.63, 37.68, 39.59, 42.59, 42.87, 75.40, 75.41, 123.53, 125.12, 126.85, 128.70, 130.60, 130.85, 134.58, 149.91, 164.23, 186.61. 19F NMR (376MHz, CDCI3) δ-61.98, -61.96, -61.93. HRMS (ESI): calcd. for C39H55F3Na04: 667.3938, found: 667.3945.


x) 3,3,3-trifluoro-2-methyl-l-phenyIpropan-l-one (Scheme 4; entry 4a)4.
Trifluoromethylation was done by general procedure A with β methyl styrene (0.25mmol, 31 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); colourless liquid; isolated yield: 92% (46.5 mg). 1H NMR (400 MHz, Chloroform-d) δ1.37 -1.56 (d, J= 7.1 Hz, 3H), 4.20-4.32 (dddd,7 = 15.1, 8.0, 7.1, 0.9 Hz, IH), 7.48-7.55 (m, 2H), 7.60 - 7.67 (m, IH), 7.92 - 8.01 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 11.86, 44.38, 44.64, 124.14, 126.92, 128.80, 129.11, 134.19, 194.61.19F NMR (376 MHz, CDC13) l-62.08,-62.11.

y) (S)-2-(trifluoromethyl)-3,4-dihydronaphthalen-l(2H)-one (Scheme 4; entry 4b)5.
Trifluoromethylation was done by general procedure A with 1,2-dihydronaphthalene (0.25mmol, 33 uL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); colourless liquid; isolated yield: 85% (45.5 mg). 'H NMR (400 MHz, Chloroform-d) δ 2.21 - 2.33 (dddd, 7 = 13.5, 11.9, 10.0, 5.6 Hz, IH), 2.46-2.54 (dq, 7- 13.8, 4.6, 4.6, 4.6 Hz, 1H), 3.06 - 3.12 (dt, 7 = 9.5, 4.8, 4.8 Hz, 2H), 3.22 - 3.33 (dqd, 7 = 11.9, 8.8, 8.8, 8.8, 4.5 Hz, IH), 7.24 - 7.31 (m, 1H), 7.32 - 7.38 (tdt, 7 = 7.3, 7.3, 1.3, 0.7, 0.7 Hz, IH), 7.50 - 7.56 (td, 7 =7.5, 7.5, 1.5 Hz, 1H), 8.04 - 8.09 (dd, J= 7.9, 1.4 Hz, IH). 13C NMR (101 MHz, CDCl3) δ 41.84, 42.12, 42.40, 42.68, 122.84, 128.54, 129.14, 134.42, 138.99, 189.95. I9F NMR (376 MHz, CDC13) δ -67.55, -67.53.

z) (S)-2-(trifluoromethyl)-2,3-dihydro-lH-inden-l-one (Scheme 4; entry 4c)5.
Trifluoromethylation was done by general procedure A with lH-indene (0.25mmol, 30 μL) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (1:99 v/v); colourless liquid; isolated yield: 82% (41 mg). 1H NMR (400 MHz, Chloroform-d) 5 3.27 - 3.37 (m, 1H), 3.38 - 3.51 (m, 2H), 7.39 - 7.47 (t, J = 7.5, 7.5 Hz, IH), 7.50 - 7.55 (d, J= 7.7 Hz, IH), 7.63 -7.71 (td, 7=7.5, 7.4, 1.2 Hz, 1H), 7.79-7.85 (d, 7= 7.7 Hz, 1H). 13C NMR (101 MHz, CDC13) δ 14.33, 49.52, 49.79, 50.06, 50.34, 123.73, 124.89, 126.50, 126.71, 128.37, 136.02, 152.29, 197.09.19F NMR (376 MHz, CDCl3) δ -67.76, -67.73


aa) 3,3,3-trifluoro-l,2-diphenylpropan-l-one (Scheme 4; entry 4d)6. Trifluoromethylation was done by general procedure A with (E)-l,2-diphenylethene (0.25mmol, 45 mg) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (2:99 v/v); colourless liquid; isolated yield: 65% (43 mg). 1H NMR (400 MHz, Chloroform-d) δ 5.23 - 5.35 (q, J = 8.2, 8.2, 8.2 Hz, 1H), 7.35 - 7.44 (m, 5H), 7.45 - 7.49 (dd, J= 7.4, 2.2 Hz, 2H), 7.50 - 7.57 (m, 1H), 7.89 - 7.92 (m, 2H). 13C NMR (101 MHz, CDC13) δ 56.36, 56.62, 56.89, 57.04, 128.99, 129.01, 129.41, 129.50, 129.84, 129.86, 130.04, 134.01, 191.30. 19F NMR (376 MHz, CDCl3)δ -61.51,-61.53.

ab) l-(benzo[b]thiophen-3-yl)-3,3,3-trifluoropropan-l-one (Scheme 5; entry 5a).
Trifluoromethylation was done by general procedure A with 3-vinylbenzo[b]thiophene(0.25 mmol, 40 mg) as the substrate. Pure trifluoromethylated 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: 86% (52.5 mg). 1H NMR (400 MHz, Chloroform-d) δ 3.76-3.86 (q, ,7=10.1, 10.1, 10.1 Hz, 2H), 7.43-7.49 (ddd, .J=8.3, 7.1, 1.4 Hz, 1H), 7.50 - 7.56 (m, 1H), 7.86 - 7.90 (m, 1H), 8.27 - 8.31 (s, 1H), 8.75 - 8.80 (dt, J= 8.2, 1.0, 1.0 Hz, 1H). 13C NMR (101 MHz, CDC13) δ 43.83, 44.11, 122.50, 125.83, 126.21, 126.54, 134.51, 136.34, 138.96, 139.88, 184.40. 19F NMR (376 MHz, CDCl3) δ-61.83,-61.81,-61.80,-61.78. m.p. 72-76 °C.

ac) 3,3,3-trifluoro-l-(3-methyl-l-phenyl-lH-pyrazol-4-yl)propan-l-one (Scheme 5; entry 5b). Trifluoromethylation was done by general procedure A with 3-methyl-l-phenyl-4-vinyl-l-pyrazole (0.25 mmol, 46 mg) as the substrate. Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: ethyl acetate/ petroleum ether (5:95 v/v); yellow liquid; isolated yield: 42% (28mg). 1H NMR (400 MHz,

Chloroform-d) 5 2.57 - 2.61 (s, 3H), 3.54 - 3.63 (q, J= 10.3, 10.3, 10.3 Hz, 2H), 7.34 - 7.40 (m, 1H), 7.46-7.52 (m, 2H), 7.65 - 7.71 (m, 2H), 8.27 - 8.32 (s, 1H). 13C NMR (101 MHz, CDCI3) δ 14.45, 44.64, 44.92, 119.89, 122.65, 125.41, 128.00, 129.89, 131.20, 139.12, 153.05, 183.79. I9F NMR (376 MHz, CDC13) δ -61.87, -61.85, -61.83. HRMS (ESI): calcd. for C13H11F3N2O: 301.0458, found: 301.0447

ad) l-(dibenzo[b,d]thiophen-4-yl)-3,3,3-trifluoropropan-l-one (Table 5; entry 5c).
Trifluoromethylation was done by general procedure A with 4-vinyldibenzo[b,d]thiophene(0.25 mmol, 52.5 mg) as the substrate. Pure trifluoromethylated 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: 62% (45.6 mg). 1H NMR (400 MHz, Chloroform-d) δ 4.21 - 4.30 (q,J= 10.0, 9.9, 9.9 Hz, 2H), 7.40 - 7.50 (m, 2H), 7.52 - 7.59 (ddd, J= 8.4, 7.3, 1.3 Hz, 1H), 7.65 - 7.70 (dt, J= 8.3, 0.9, 0.9 Hz, 1H), 7.97 - 8.03 (ddd, J= 7.7, 1.4, 0.7 Hz, 1H), 8.08 - 8.13 (dd,y= 7.8, 1.3 Hz, 1H), 8.17-8.21 (dd,J= 7.6, 1.4 Hz, 1H). 13C NMR (101 MHz, CDCI3) δ 46.10, 46.37, 46.65, 46.93, 112.14, 121.08, 122.93, 123.14, 123.37, 124.02, 126.25, 126.83, 128.03, 128.45, 154.62, 156.14, 187.88.19F NMR (376 MHz, CDCI3) δ-66.54,-66.52, -62.50. HRMS (ESI): calcd. for C5H9F3O2: 301.0458, found: 301.0447. m.p. 122 °C.

ae) 3,3,3-trifluoro-l-(l-p-tolyl-lH-indazol-5-yl)propan-l-one (Table 5; entry 5d)1.
Trifluoromethylation was done by general procedure A with l-p-tolyl-5-vinyI-1H-indazole (0.25 mmol, 58.5 mg) as the substrate. Pure trifluoromethylated 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: 75% (62 mg). 1H NMR (400 MHz, Chloroform-d) 5 2.43-2.48 (s, 3H), 3.84 - 3.94 (q, J = 10.0, 10.0, 10.0 Hz, 2H), 7.35 - 7.38 (d, J= 8.2 Hz, 2H), 7.54-7.61 (m, 2H), 7.71 - 7.76 (dt,J= 8.9, 0.9, 0.9 Hz, 1H), 8.02 - 8.07 (dd, J= 9.0, 1.7 Hz, 1H), 8.31 -8.36(111, 1H), 8.40- 8.44 (m, 1H). 13C NMR (101 MHz, CDC13) δ 21.35, 41.90, 42.19, 42.47, 42.75, 111.16, 123.22, 124.36, 124.95, 126.74, 130.12, 130.40, 137.02, 137.15, 137.87, 140.98, 188.98. 19F NMR (376 MHz, CDCl3) δ -61.84, -61.82, -61.81. HRMS (ESI): calcd. for C17H13F3N2O: 301.0458, found: 301.0447. m.p. 142 °C.


af) l-cyclohexyl-3,3,3-trifluoropropan-l-one (Scheme 5; entry 5e). Trifluoromethylation was done by general procedure A with vinylcyclohexane (0.25 mmol, 33 μL) as the substrate and and K2S2O8 (O.lOmmol, 27 mg). Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Eluent: dichloromethane/petroleum ether (5:95 v/v); colourless liquid; isolated yield: 81% (39 mg). 1H NMR (400 MHz, Chloroform-d) 1.17- 1.42 (m, 6H), 1.65-1.72 (m, 1H), 1.77-1.91 (m, 4H), 2.36-2.45 (tt, J = 11.1, 11.1,3.3,3.3 Hz, 1H), 3.21 -3.31 (q,J= 10.3, 10.3, 10.3 Hz, 2H). 13C NMR (101 MHz, cdcl3) δ 25.60, 25.86, 28.17, 43.67, 43.94, 44.22, 44.50, 51.47, 125.41, 203.33. 19F NMR (376 MHz, CDC13) δ -62.38, -62.36, -62.32.

ag) l-cyclooctyl-3,3,3-trifluoropropan-l-one(Scheme 5; entry 5f). Trifluoromethylation was done by general procedure A with vinylcyclooctane (0.25 mmol, 44 uL) as the substrate and K2S208 (O.lOmmol, 27 mg). Pure trifluoromethylated product was isolated by column chromatography through a silica gel column (mesh 60-120). Dichloromethane/ petroleum ether (5:95 v/v); colourless liquid; isolated yield: 85% (47 mg). lH NMR (400 MHz, Chloroform-d) δ 0.82-0.91 (m, 2H), 1.22- 1.30 (m, 1H), 1.41 - 1.67 (m, 8H), 1.67 - 1.86 (m, 3H), 2.59-2.67 (ddd, J= 9.0, 5.4, 3.6 Hz, 1H), 3.21 - 3.31 (q, J = 10.3, 10.3, 10.3 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 22.88, 25.48, 26.39, 26.72, 27.62, 31.81, 43.88, 44.16, 44.43, 44.71, 5.1.50, 125.40, 203.68. 19F NMR (376 MHz, CDC13) δ -62.41, -62.39, -62.36. HRMS (ESI): calcd. for C11H17F3NaO: 245.1127, found: 245.1124.
The examples disclosed herein above are only illustrative. Obvious alterations and modifications known to persons skilled in the art are not excluded from the scope and ambit of this invention and the appended claims.

WE CLAIM:
1. A process for trifluoromethylation comprising the steps of reacting olefins with sodium triflinate NaS02CF3 (Langlois Reagent) in the catalytic presence of Ag/K2S2O8 and in a solvent medium of DMF either alone or in admixture with water in the presence of atmospheric oxygen and recovering a-Trifluoromethyl ketone from the reaction mixture.
2. The process as claimed in claim 1, wherein the olefins are aromatic and heteroaromatic olefins which are unactivated.
3. The process as claimed in claims 1 and 2 wherein the aromatic or heteroaromatic groups may be substituted by functional groups as herein described.
4. The process as claimed in claim 1 wherein the reaction mixture is separated by column chromatography in a silica gel column.
5. The process as claimed in claim 4 wherein a-Trifluoromethyl Olefins are eluted by solvents such as ethers and ethyl acetate.
6. The process as claimed in claim 1 being carried out at ambient temperature.
7. The process as claimed in claim 1 wherein said reaction is carried out with 2 equivalents triflinate and 0.2 equivalent of the catalyst AgNO3/K2S2O8.
8. The process as claimed in claim 1 wherein the following compounds are synthesized

a) 3,3,3-trifluoro-l-phenylpropan-l-one
b) 3,3,3-trifluoro-1-p-tolylpropan-l-one
c) 3,3,3-trifluoro-l-(4-methoxyphenyl)propan-l-one
d) 3,3,3-trifluoro-1 -(4-fluorophenyl)propan-1 -one
e) l-(4-chlorophenyi)-3,3,3-trifluoropropan-l-one
f) 1 -(4-bromophenyl)-3,3.3-trif]uoropropan-1 -one

g) 4-(3,3,3-trifluoropropanoyl) benzonitrile
h)3,3,3-trifluoro-l-(4-nitrophenyi)propan-l-one
i) methyl 4-(3,3,3-trifluoropropanoyl)benzoate
j) 3,3,3-trifiuoro-l-m-tolyIpropan-l-one
k)3-(3,3,3-trifluoropropanoyl)benzaldehyde
l)3,3,3-trifluoro-l-(3-nitropheny!)propan-l-one
m) l-(4-(chloromethyl)phenyl)-3,3,3-trifluoropropan-l-one
n) l-(2-chloropheny|)-3,3,3-trifluoropropan-1-one
o) l-(2-bromophenyl)-3,3,3-trifluoropropan-l-one
p)3,3,3-trifluoro-l-o-tolylpropan-l-one
q)3,3,3-trifluoro-l-(naphthalen-2-yI)propan-l-one
r) 3,3,3-trifluoro-1 -(naphthalen-1 -yl)propan-1 -one
s) allyl 4-(3,3,3-trifluoropropanoyl)benzoate
t) prop-2-ynyl 4-(3,3,3-trifiuoropropanoyl)benzoate
u)(lS,5S)-4,6,6-trimethyIbicycIo[3.1.1]hept-3-en-2-yl4-(3,3,3-trifluoropropanoyl)benzoate
v)3,3,34rifluoro-l-(4-{{3-phenyl-lH-pyrazol-l-yl)methyl)phenyl)propan-l-one
x)3,3,3-trifluoro-2-methyl-l-phenyipropan-l-one
w) (R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl-4-(3,3,3-trifluoropropanoyl)benzoate
y) 3,3,3-trifluoro-2-methy]-l-phenylpropan-l-one
z) (S)-2-(trifluoromethyl)-3,4-dihydronaphthalen-l (2H)-one
(S)-2-(trifluoromethyl)-2,3-dihydro-lH-inden-l-one
k) 3,3,3-trifluoro-l,2-diphenylpropan-l-one
l) l-(benzo[b]thiophen-3-yl)-3,3,3-trifluoropropan-l-one ac)3,3,3-trifluoro-l-(3-methyl-l-phenyl-lH-pyrazol-4-yl)propan-l-one

m) l-(dibenzo[b,d]thiophen-4-y!)-3,3,3-trifluoropropan-l-one
n) 3,3,3-trifluoro-1 -(1 -p-tolyl-1 H-indazol-5-yl)propan-1 -one
o) l-cyclohexyl-3,3,3-trifIuoropropan-l-one
p) l-cyclooctyl-3,3,3-trifluoropropan-l-one
9. α-Trifluoromethy] Ketones whenever produced by a process as claimed in claims 1 to 7.