Nitrogen-containing monodentate phosphines and
their use in catalysis
Description:
The present invention relates to novel ligands for
transition metals, to their preparation and to their use in
catalytic reactions, especially for the improvement of
haloaromatic compounds.
Haloaromatic compounds, including especially chloroaromatic
compounds, are intermediates which can be used variously in
the chemical industry and which serve as preliminary
products for the production of agricultural intermediates,
Pharmaceuticals, colourings, materials, etc. . Vinyl halides
are also important intermediates which are used as starting
materials for polymers and in the production of the above-
mentioned products.
Catalysts which are frequently employed for the
functionalisation of haloaromatic compounds or vinyl
halides to aromatic olefins or dienes (Heck reaction,
Stille reaction) , biaryls (Suzuki reaction), alkynes
(Sonogashira reaction), carboxylic acid derivatives (Heck
carbonylation) , amines (Buchwald-Hartwig reaction) are
palladium catalysts and nickel catalysts. Palladium
catalysts are generally advantageous, owing to the wide
applicability of coupling substrates with in some cases
good catalytic activities, while nickel catalysts have
advantages in the field of the reaction of chloroaromatic
compounds and vinyl chlorides. Moreover, nickel is more
readily available than palladium.
Palladium and nickel catalysts used within the scope of the
activation and further improvement of haloaromatic
compounds are both palladium(II) and/or nickel(II)
complexes as well as palladium(0) and/or nickel(0)

complexes, although it is known that palladium (0) and
nickel (0) compounds are the actual catalysts of the
reaction. In particular, according to information in the
literature, coordinatively unsaturated 14- and 16-electron
palladium(O) and nickel (0) complexes stabilised with donor
ligands such as phosphanes are formulated as the active
species.
When iodides are used as starting materials in coupling
reactions it is also possible to dispense with phosphane
ligands. However, aryl iodides and vinyl iodides are
starting materials which are scarcely available and
therefore very expensive, and their reaction additionally
yields stoichiometric amounts of iodine salt waste
products. If other starting materials are used in the Heck
reaction, such as aryl bromides or aryl chlorides, the
addition of stabilising and activating ligands is necessary
if catalytically effective reaction of the starting
materials is to be possible.
The catalyst systems described for olefinations,
alkynylations, carbonylations, arylations, aminations and
similar reactions frequently have satisfactory catalytic
turnover numbers (TON) only with uneconomical starting
materials such as iodoaromatic compounds and activated
bromoaromatic compounds. Otherwise, in the case of
deactivated bromoaromatic compounds and, especially, in the
case of chloroaromatic compounds, large amounts of catalyst
- usually more than 1 mol. % - must generally be added in
order to achieve industrially usable yields (> 90 %) -
Moreover, owing to the complexity of the reaction mixtures,
simple recycling of the catalyst is not possible, so that
recovery of the catalyst also gives rise to high costs,
which generally stand in the way of industrial
implementation. Furthermore, it is undesirable to work with
large amounts of catalyst, especially when preparing active
ingredients or preliminary products for active ingredients,

because catalyst residues otherwise remain in the product
in this case.
More recent active catalyst systems are based on
cyclopalladated phosphanes (W. A. Herrmann, C. Brofimer,
K. Öfele, C.-P. Reisinger, T. Priermeier, M. Beller,
H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int.
Ed. Engl. 1995, 34, 1844) or mixtures of sterically
demanding arylphosphanes (J. P. Wolfe, S. L. Buchwald,
Angew. Chem. 1999, 111, 2570; Angew. Chem. Int. Ed. Engl.
1999, 38, 2413) or tri-tert.-butylphosphane (A. F. Littke,
G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int.
Ed. Engl. 1998, 37, 3387) with palladium salts or palladium
complexes.
However, chloroaromatic compounds can generally not be
activated in an industrially satisfactory manner even using
these catalysts. Accordingly, in order to achieve high
yields, comparatively large amounts of catalyst must be
used. Therefore, despite all the further developments which
have been made to catalysts in recent years, only a small
number of industrial reactions of the arylation,
carbonylation, olefination, etc. of chloroaromatic
compounds have hitherto become known.
For the mentioned reasons, the object underlying the
present invention was to provide novel ligands and
catalysts which are suitable for large-scale applications,
are readily accessible and convert chloro- and bromo-
aromatic compounds as well as corresponding vinyl compounds
to the respective coupling products in high yield and with
high purity, with high catalyst productivity.
This object is achieved according to the invention by novel
phosphane ligands of formula (I)


wherein
X independently of Y represents a nitrogen atom or a
C-R2 group and
Y independently of X represents a nitrogen atom or a
C-R9 group,
R for each of the two R1 groups independently of the
other represents a radical selected from the group
C1-C24-alkyl,
c3-C20-cycloalkyl, which includes especially both
monocyclic and also bi- and tri-cyclic cycloalkyl
radicals,
C5-C14-aryl, which includes especially the phenyl,
naphthyl, fluorenyl radical,
c2-C13-heteroaryl, wherein the number of hetero atoms,
selected from the group N, o, S, may be from 1 to 2,
wherein the two radicals R1 may also be linked to one
another, there preferably being formed a 4- to 8-
membered saturated, unsaturated or aromatic ring.
The above-mentioned radicals R1 may themselves each be
mono- or poly-substituted. These substituents,
independently of one another, may be hydrogen, C1-C20-
alkyl, C2-C20-alkenyl, C3-C8-cycloalkyl, C2-C9-hetero-
alkyl, C5-C10-aryl, C2-C9-heteroaryl, wherein the
number of hetero atoms, especially from the group N,

0, S, may be from 1 to 4, C1-C20-alkoxy, preferably
C1-C10-alkoxy, particularly preferably OMe, C1-C10-halo-
alkyl, preferably trifluoromethyl, hydroxy, secondary,
tertiary amino groups of the forms NH- (C1-C20-alkyl),
NH- (C5-C10-aryl) , N (C1-C20-alkyl) 2, N {C1-C20-
alkyl) (C5-C10-aryl), N(C5-C10-aryl)2, N(C1-C20-
alkyl/C5-C10-aryl3)3+, NH-CO-C1-C20-alkyl, NH-CO-C5-C10-
aryl, carboxylato of the forms COOH and COOQ (wherein
Q represents either a monovalent cation or C1-C8-
alkyl), C1-C6-acyloxy, sulfinato, sulfonato of the
forms SO3H and SO3Q (wherein Q represents either a
monovalent cation, C01-C20-alkyl or Cs-C10-aryl) , tri-
C1-C6-alkylsilyl, especially SiMe3,
wherein two of the mentioned substituents may also be
bridged with one another, there preferably being
formed a 4- to 8-membered ring which can be further
substituted preferably by linear or branched C1-C10-
alkyl, C6-aryl, benzyl, C1-C10-alkoxy, hydroxy or
benzyloxy groups.
R2-R9 represent a hydrogen, alkyl, alkenyl, cycloalkyl,
aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N-
(alkyl)2, O-(aryl), NH-(aryl), N-(alkyl)(aryl), O-C0-
alkyl, o-CO-aryl, F, Si(alkyl)3, CF3, CN, CO2H, COH,
SO3H, CONH2, CONH (alkyl), C0N(alkyl)2, SO2 (alkyl),
SO(alkyl), SO(aryl), SO2(aryl), SO3(alkyl), SO3(aryl),
S-alkyl, S-aryl, NH-CO(alkyl), CO2(alkyl), CONH2,
CO(alkyl), NHCOH, NHCO2 (alkyl), CO(aryl), Co2(aryl)
radical,
wherein two or more adjacent radicals, each
independently of the other(s), may also be linked to
one another so that a condensed ring system is present
and
wherein in R2 to R9

alkyl represents a hydrocarbon radical having from 1
to 20 carbon atoms which may in each case be linear or
branched, alkenyl represents a mono- or poly-
unsaturated hydrocarbon radical having from 2 to 20
carbon atoms which may in each case be linear or
branched, and cycloalkyl represents a hydrocarbon
having from 3 to 20 carbon atoms, wherein the alkyl,
alkenyl and cycloalkyl groups may also carry further
substituents as defined for R1. Preferred substituents
in this connection are selected from the group Br, Cl,
F, (C1-C12)-alkyl, O-(C1-C12)-alkyl, phenyl, O-phenyl,
NH((C1-C12)-alkyl), N( (C1-C12)-alkyl) 2, and
aryl represents a 5- to 14-membered aromatic radical .
in which from one to four carbon atoms may also be
replaced by hetero atoms from the group nitrogen,
oxygen and sulfur so that a 5- to 14-membered hetero-
aromatic radical is present and wherein the aryl or
heteroaryl radical may carry further substituents as
defined for R1, preferred substituents being selected
from the group Br, Cl, F, (C1-C12) -alkyl, O-(C1-C12)-
alkyl, phenyl, O-phenyl, NH2/ NH( (C1-C12)-alkyl) ,
N((C1-C12)-alkyl)2.
The mentioned alkyl radicals have preferably from 1 to 10
carbon atoms, particularly preferably from 1 to 5. The
alkenyl radicals have preferably from 2 to 10 carbon atoms,
particularly preferably from 2 to 5. The cycloalkyl
radicals have preferably from 3 to 8 carbon atoms. The aryl
radicals have preferably from 6 to 10 carbon atoms, the
heteroaryl radicals from 4 to 9.
Preference is given to ligands wherein X is CR and Y is
CR9, yielding compounds of formula (IT)


wherein the radicals R1 to R9 are as defined above. In a
further preferred embodiment, X is nitrogen and Y is a CR9 .
group.
Preferred ligands of formula (I) or (II) carry at least one
radical R1 selected from the group consisting of phenyl,
C1-C10-alkyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-
adamantyl, 2-adamantyl, 5H-dibenzophospholyl, 9-phospha-
bicyclo[3.3.1]nonanyl, 9-phosphabicyclo[4.2.1]nonanyl
radicals. Examples of preferred Ci-C10-alkyl radicals are
methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl-
propyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-
methylbutyl, 3-methylbuty1, 2,2-dimethylpropyl, 1-ethyl-
propyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-
methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl-
pentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl-
butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethyl-
butyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1 - ethyl-1-me thylpropyl, n-heptyl, n-
octyl, n-nonyl, n-decyl, particular preference being given
especially to the isopropyl radical and the tert.-butyl
radical.
Preferred radicals R2 to R9 are selected from the group
hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C1-C10-haloalkyl,
C3-C8-cycloalkyl, C6-C10-aryl, which includes especially

also phenyl, naphthyl, fluorenyl, and C2-C6-heteroaryl,
wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur
atom may be present as hetero atom,
and wherein two adjacent radicals R2 to R9 may be bridged
with one another, there preferably being formed a 4- to 8-
membered, preferably aromatic ring.
The ligands according to the invention can be prepared by
reacting the corresponding phenylpyrrole derivative in the
presence of a strong base, such as, for example, an alkyl-
lithium compound, and subsequently adding a halophosphane,
in accordance with the following reaction scheme, which is
given by way of example

According to the invention, the novel phosphane ligands are
used as catalysts in combination with transition metal
complexes or transition metal salts of sub-group VIII of
the periodic system of the elements, such as, for example,
palladium, nickel, platinum, rhodium, iridium, ruthenium,
cobalt. The ligands according to the invention can
generally be added in situ to corresponding transition
metal precursor compounds and accordingly used for
catalytic applications. However, it may occasionally be
advantageous for specific mono-, di-, tri- or tetra-
phosphane complexes of the mentioned transition metals to
be prepared first and subsequently used for catalysis

reactions. The catalytic activity can thereby be increased
further in some catalyst systems.
As transition metal compounds there are preferably used
palladium or nickel compounds and particularly preferably
palladium compounds.
The ligands according to the invention are generally added
in situ preferably to nickel(II) or palladium(II) salts or
to nickel(II), palladium(II) or nickel(O) or palladium(O)
complexes. Preferred palladium complexes are, for example,
palladium (II) acetate, palladium (II) chloride,
palladium(II) bromide, lithium tetrachloropalladate(II),
palladium(II) acetylacetonate, palladium(0)-dibenzylidene-
acetone complexes, palladium(O) tetrakis(triphenyl-
phosphane), palladium(O) bis(tri-o-tolylphosphane),
palladium(II) propionate, palladium(II) bis(triphenyl-
phosphane) dichloride, palladium(O) diallyl ether
complexes, palladium(II) nitrate, palladium(II) chloride
bis(acetonitrile), palladium(II) chloride bis(benzo-
nitrile).
In catalytic applications, the phosphane ligand is
generally used in excess relative to the transition metal.
The ratio of transition metal to ligand is preferably from
1:1 to 1:1000. Ratios of transition metal to ligand of from
1:1 to 1:100 are particularly preferred. The exact
transition metal/ligand ratio to be used depends on the
concrete application, but also on the amount of catalyst
used. Accordingly, it is generally customary to use low
transition metal/ligand ratios at very low transition metal
concentrations (< 0.01 mol.%) than at transition metal
concentrations of from 0.5 to 0.01 mol.% transition metal.
The catalysts are preferably used at temperatures of from
20 to 200°C; in many cases, it has proved advantageous to
work at temperatures of from 3 0 to 180°C, preferably from

40 to 160°C. The ligands can also be used without any loss
of activity in reactions under pressure, reactions usually
being carried out only up to a pressure of 100 bar, but
preferably in the range of from normal pressure to 60 bar.
When carrying out catalytic reactions using ligands of
formula (I), high turnover rates (TON) can be achieved with
a low catalyst concentration. The transition metal is
preferably used in a ratio of from 5 mol.% to 0.001 mol.%,
particularly preferably from 0.5 mol.% to 0.01 mol.%,
relative to the substrate.
The phosphane ligands prepared in accordance with the
invention have proved suitable especially as the ligand
component for the catalytic preparation of arylated olefins
(Heck reactions) , biaryls (Suzuki reactions) , α-aryl
ketones and amines from aryl halides or vinyl halides.
However, it is obvious to the person skilled in the art
that the novel catalyst systems can also be used to
catalyse other transition-metal-catalysed reactions, such
as metathesis or hydrogenations of double bonds or carbonyl
compounds, but especially palladium- and nickel-catalysed
carbonylations of aryl halides, alkynylations using alkynes
(Sonogashira couplings), cross-couplings using
organometallic reagents, such as, for example, zinc
reagents or tin reagents.
A particular advantage of the ligands according to the
invention is the high degree of activity induced by the
ligands in the activation of readily available but inert
chloroaromatic compounds. The described catalyst and ligand
systems can accordingly be used for large-scale purposes.
The phosphanes prepared in accordance with the invention
can be used in the preparation of aryl olefins, dienes,
diaryls, benzoic acid derivatives, acrylic acid
derivatives, arylalkanes, alkynes, amines. The compounds so

prepared are used, for example, as UV absorbers, as
intermediates for Pharmaceuticals and agrochemicals, as
ligand precursors for metallocene catalysts, as perfumes,
as active ingredients having biological activity and as
structural units for polymers.
Implementation Examples :
General
Reactions of compounds sensitive to air were carried out in
an argon-filled glove-box or in standard Schlenk tubes. The
solvents tetrahydrofuran (THF), diethyl ether and
dichlorome thane were degassed and rendered absolute by
means of a solvent-drying installation (Innovative
Technologies) by filtration through a column packed with
activated aluminium oxide. Toluene and pentane were
additionally freed of oxygen using a column packed with a
copper catalyst.
The Examples which follow serve to explain the invention
without limiting it thereto.
Preparation of ligands 1 to 3 (L1 to L3):
10 mmol. of phenylpyrrole are dissolved under argon in
20 ml of absolute hexane. 10 mmol. of TMEDA and 10 mmol. of
n-BuLi (1.6 M in hexane) are added at room temperature.
After three hours' heating under reflux, a yellow
suspension is obtained. It is cooled to room temperature,
and 10 mmol. of Cl-PRS are slowly added thereto. After
reacting for one hour under reflux, hydrolysis is carried
out at room temperature using 15 ml of degassed water. The
organic phase is transferred to a separating funnel, under
argon, with the aid of a cannula. The aqueous phase is
extracted twice using 15 ml of hexane each time. The hexane

fractions are likewise transferred to the separating
funnel. The combined organic phases are washed with 15 ml
of degassed water and dried over degassed sodium sulfate.
The solvents are distilled off and the viscous residue is
dissolved in methanol with heating. After one day at room
temperature, the mixture is cooled for four hours at 0°C.
The resulting white solid is filtered off and dried in
vacuo (purity 90-95 %).
Yields:
PR12 = PCy2 72 % (31P-NMR: -28.0 ppm) (Ll; N-PHOS-Cy)
PR12 = PPh2 64 % (31P-NMR: -29.8 ppm) (L2; N-PHOS-Ph)
PR12 = PTBu2 40 % (31P-NMR: 3.6 ppm) (L3; N-PHOS-cBu)
Catalysis Examples 1 to 32: Suzuki couplings
1.25 mmol. of phenylboronic acid and 2.00 mmol. of base are
weighed into 2.5 ml glass bottles. These bottles are purged
with argon and sealed. All further stock solutions are
prepared under argon.
Solution S-l: 147 mmol. of 2-chlorotoluene, 58 mmol. of
tetradecane, 155 ml of abs. toluene
Solution S-2: 150 mmol. of 4-chloroanisole, 57 mmol. of
tetradecane, 154 ml of abs. toluene
Solution M-l: 0.073 mmol.Pd of palladium(II) acetate, 49 ml
of abs. toluene
Solution M-2: 0.065 mmol.Pd of tris- (dibenzylideneacetone -
dipalladium(O), 49 ml of abs. toluene
Solution L-l: 0.04 mmol. of N-PHOS-Cy (Ll), 10 abs. toluene
Solution L-2: 0.08 mmol. of N-PHOS-tBu (L3), 21 abs.
toluene
The following solutions are mixed under Ar and stirred for
about 1 hour at room temperature (reaction metal precursor
with ligand):


A Vantage synthesizer is used to pipette the following
amounts of the resulting solutions into the Vantage vials:
1. 1.25 ml of S-l (No. 1-8), (No. 17-24)
1.25 ml of S-2 (No. 9-16), (No. 25-32)
2. 1.25 ml of M-L-l (No. 1-16) or 1.25 ml of M-L-2
(No. 17-32).
Using the Vantage mixing/heating unit, the Vantage vials so
filled are heated for 4.0 hours at 110°C (Vantage setting)
with shaking (1000 rpm) (heating phase 0.5 h/internal
temperature about 120°C).
After the reaction, 1.0 ml of each reaction solution is
filtered over silica gel. The solution so obtained is
analysed by means of GC. The yields of the individual,
conversions are summarised in Table 1.

Catalysis Examples 33 to 59:
Suzuki reaction of aryl chlorides with phenylboronic acid/-
pyrrolylphosphanes
R-Ar-Cl + PhB(OH)2 - R-Ar-Ph
Reagents: 3 mmol. of ArCl, 4.5 mmol. of PhB(OH)2, 6 mmol.
of K3PO4, Pd(OAc)2, Pd/L = 1:2, 6 ml of toluene, 20 hours.
The reaction is carried out as a one-pot reaction under
protecting gas. Working-up is carried out with 10 ml of
each of methyl ene chloride and IN sodium hydroxide
solution. The reaction is monitored by means of GC,
internal GC standard: hexadecane.
The starting materials used and the results of the '
conversions are summarised in Table 2.

Examples 60 to 64: Examples of ligand syntheses
Example 60: Synthesis of iV-phenyl-2- (di-1-adamantyl-
phosphino)pyrrole

1.6 ml of TMEDA (15 mmol.) are added to a suspension of
1.43 g (10 mmol.) of N-phenylpyrrole in 30 ml of hexane.
6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are
added at room temperature. The mixture is then heated for
2.5 hours at reflux temperature (solution 1). In another
flask, 3.36 g (10 mmol.) of di-1-adamantylchlorophosphane
are mixed with 40 ml of hexane and heated to 76°C
(solution 2) . The boiling solution 1 is then slowly
transferred into solution 2, which is at 76°C, by means of
a cannula. The mixture is then boiled for a further 2 hours
at reflux, the solution is cooled, and 20 ml of water are
added thereto. The organic phase is filtered off over
magnesium sulfate. The solution is concentrated in vacuo;
15 ml of toluene are added thereto, and the mixture is
heated to 60°C and then cooled. After one day at room
temperature, the product is filtered off. Yield: 3.3 g
(75 %).
31P NMR (161 MHz, CDC13) : δ = -4.5.
XH NMR (400 MHz, CDCl3): δ = 1.7 (bs, 16H) , 1.7-2.0 (m,
22H) , 6.4 (dd, J1 = 8.6, 12.8, J2 = 3.5, 1H) , 6.75 (dd, Jx =
3.5, J2 = 1, 1H) , 6.9-7.0 (m, 1H) , 7.25-7.3 (m, 2H) ,
7.35-7.45 (m, 3H).
13C NMR (100.6 MHz, CDCl3): δ = 28.6 (d, JPC = 11.5), 37,
37.5 (d, JPC = 17.2), 41.6 (d, JPC = 11.5), 108.2, 119.5

(d. JPC = 4.7), 125.8, 126 (d, JPC = 10.8), 127.3, 128.2,
128.3 (d, JPC = 3.8), 141.6 (d, JPC = 1.9).
MS: m/z (%): 443 (68), 308 (13), 172 (14), 135 (100), 107
(7), 93 (19), 79 (17) .
HRMS: C30H38NP: calc. 443.2742; found 443.26775.
Example 61: Synthesis of l-mesityl-2- (dicyclohexyl-
phosphino)imidazole

1.6 ml of TMEDA (15 mmol.) are added to a suspension of
1.86 g (10 mmol.) of N-mesitylimidazole in 30 ml of hexane.
6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are
added at room temperature. The mixture is then heated for
2.5 hours at reflux temperature (solution 1). In another
flask, 2.2 ml (10 mmol.) of dicyclohexylchlorophosphane are
mixed with 20 ml of hexane and heated to 60°C (solution 2) .
The boiling solution 1 is then slowly transferred into
solution 2, which is at 60°C, by means of a cannula. The
mixture is then boiled for a further 1 hour at reflux, the
solution is cooled, and 20 ml of degassed water are added
thereto. The organic phase is filtered off over magnesium
sulfate. The solution is concentrated in vacuo; 30 ml of
pentane are added thereto, and the mixture is boiled for
1 hour at reflux. The product precipitates in crystalline
form at -30°C and is filtered off while cold. Yield: 2.48 g
(65 %) .
31P NMR (161 MHz, CDC13) : δ = -18.9.

1H NMR (400 MHz, CDC13) : δ = 0.9-1.2 (m, 11H) , 1.5-1.7 (m,
HH), 1.9 (S, 6H), 1.9-2.0 (m, 2H) , 2.2 (s, 3H) , 6.8-6.9
(m, 3H), 7.3 (s, 1H).
13C NMR (100.6 MHz, CDCl3) : δ = 18.5, 20.9, 26.9, 27.5, 27.7
(d, J = 9.5), 30.4 (d, J = 14.3), 30.9 (d, J = 10.5), 34.6
(d, J= 9.5), 122.7, 129.2, 131.5, 134.9, 135.5, 138.2,
147.5 (d, J = 16.2).
MS: m/z (%): 382 (11), 299 (100), 217 (24), 202 (7), 185
(27), 83 (7), 55 (21).
Example 62: Synthesis of N- (2-methoxyphenyl) -2- (dicyclo-
hexylphosphino) pyrrole
a) Synthesis of N- (2-methoxyphenyl)pyrrole

Lit.: Faigl, F. ; Fogassy, K.; Thuner, A.; Toke, L.;
Tetrahedron 1997, 53, 4883.
10.95 g (83 mmol.) of 1 and 4.7 g (38 mmol. ) of 2 are
refluxed for 2 hours in 10 ml of glacial acetic acid. The
colour of the solution changes from yellow through red to
black. The mixture is then diluted with 75 ml of distilled
water and extracted twice with 100 ml of CH2Cl2. Na2CO3 is
added to the black organic solutions. After filtration and
concentration (20 mbar, 50°C) , a black oil is obtained and
is distilled in vacuo. Yield: 4.45 g (25.7 mmol.; 75 %) .
1H NMR (25°C, CDCl3): δ (ppm) =3.8 (s, 3H) , 6.3 (t, J =
2.2 Hz, 2H) , 7.0 (m, 4H), 7.3 (m, 2H) .

b) Synthesis of N- (2-methoxyphenyl) -2- (dicyclohexyl-
phosphino) pyrrole

3.14 ml (15 mmol.) of N,N,N',N',N"-pentamethyldiethylene-
triamine (PMDTA) are added to a solution of 1.73 g
(10 nunol.) of 1 in 3 0 ml of hexane. A solution (1.6 M in
hexane) of n-BuLi (6.25 ml, 10 mmol.) is added dropwise.
After 3 hours under reflux (75°C) , the colour of the
solution has changed from yellow to black. Without cooling
this mixture, 2.2 ml (10 mmol.) of chlorodicyclohexyl-
phosphane dissolved in 20 ml of hexane are added dropwise.
Refluxing is carried out for a further one hour. The colour
of the solution lightens to orange, and a white precipitate
forms. After cooling to room temperature, 30 ml of water
are added to the mixture. The orange organic phase is
extracted 3 times using 20 ml of hexane each time. The
combined organic phases are washed with 10 ml of water and
filtered over Na2SO4. The solvent is removed in vacuo
(45°C). The viscous orange residue is refluxed for
30 minutes in 30 ml of MeOH. On cooling to RT, the product
precipitates and is filtered off (1.1 g, 30 %).
*H NMR (25°C, C6D6) : δ (ppm) = 1.1-1-9 (m, 22H) , 3.2 (s,
3H), 7.0 (m, 4H) , 6.5-7.2 (m, 3H).
13C NMR (25°C, C6D6): 5 (ppm) = 27.2, 27.7, 27.8, 29.6,
30.9, 34.9, 55.1, 109.8, 111.8, 116.5, 116.6, 120.2, 123.6,
129.3, 130.9, 136.3, 156.0.
31P NMR (2 5°C, C6D6) : δ (ppm) = -2 6.8.

Example 63: Synthesis of N-phenyl-2- (dicyclohexyl-
phosphino)indole
a) Synthesis of N-phenylindole

Lit.: Synthesis: Klapars, A.; Antilla, J. ; Huang, X.;
Buchwald, S. J. Am. Chem. Soc. 2001, 123, 7727. Analysis:
(a) Nishio, T. J. Org. Chem. 1988, 53, 1323. (b)
Beller, M.; Breindl, C; Riermeier, T.; Tillack, A. J. Org.
Chem. 2001, 66, 1403.
0.19 g (0.1 mmol.) of Cul, 2.34 g (20 nunol.) of 1, 8.82 g
(42 mmol.) of K3PO4, 0.48 ml (4 mmol.) of 1,2-diaminocyclo-
hexane and 3.16 ml (30 mmol.) of 2 are stirred for 24 hours
at 110°C in 20 ml of dry dioxane. The mixture is then
diluted with 50 ml of ethyl acetate. The violet precipitate
is filtered off over silica gel, yielding a yellow
solution, which is concentrated in vacuo (2 0 mbar, 50°C) .
The orange oil that remains is purified by column
chromatography (silica gel, hexane/ethyl acetate 98/2).
Yield: 3.0 g (15.5 mmol.; 75 %).
1H NMR (25°C, CDCl3): δ (ppm) = 6.45 (m, 1H) , 6.9-7.5 (m,
10H) .

13C NMR (25°C, CDCl3) : δ (ppm) = 104.1, 111.1, 120.9, 121.7,
122.9, 124.9, 126.9, 128.5, 129.9, 130.1, 130.6, 132.1,
136.4, 140.3.
b) Synthesis of N-phenyl-2- (dicyclohexylphosphino) indole

1.6 ml (15 mmol.) of TMEDA are added to 1.93 g (10 mmol.)
of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-
BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours'
reflux (75°C), the colour has deepened from yellow to
orange. Without cooling, a solution of 2.2 ml (10 mmol.) of
chlorodicyclohexylphosphane in 20 ml of hexane is added
dropwise. Refluxing is carried out for a further one hour,
the colour of the mixture lightening again and a white
solid precipitating. After cooling, 30 ml of water are
added to the mixture. The aqueous phase is extracted
3 times using 20 ml of hexane each time. The combined
organic phases are washed with 10 ml of water, dried over
Na2SO4 and concentrated in vacua (45°C) . The yellow residue
is boiled for 30 minutes in 30 ml of MeOH. After cooling to
RT, the resulting product is filtered off (660 mg, 17 %).
31P NMR (25°C, C6D6) : 6 (ppm) = -24.8.

Example 64: Synthesis of N- (naphthyl) -2- (dicyclohexyl-
phosphino)pyrrole
a) Synthesis of N-naphthylpyrrole

Lit.: Analysis: (a) Paredes, E.; Biolatto, B.;
Kneeteman, M.; Mancini, P. Tetrahedron Lett. 2000, 41,
8079. (b) Gross, H. Chem. Ber. 1962, 95, 2210.
10.95 g (83 mmol.) of 1 are added to a violet solution of
5.44 g {38 mmol.) of 2 in 10 ml of glacial acetic acid. The
resulting brown solution is refluxed for 3 hours under
argon (120°C) , whereupon its colour changes to black. The
solution is concentrated to half the volume in vacuo
(20 mbar, 50°C) before being hydrolysed with 20 ml of
water. The organic phase is extracted with CH2CI2 (3 x
30 ml), dried over Na2SO4 and concentrated (20 mbar, 50°C) ,
there being obtained a black oil which is purified by
column chromatography (silica gel, hexane/ethyl acetate
85/15). Yield: 3.53 g (18.3 mmol.) of a red oil which
crystallises at -25°C (pink crystals).
2H NMR (25°C, CDCl3) : δ (ppm) = 6.3 (t, J = 2.2 Hz, 2H) , 6.7
(t, J = 2.2 Hz, 2H), 6.9-7.2 (m, 4H) , 7.3 (d, 8.1 Hz, 1H),
7.4 (d, 8.1 Hz, 1H), 7.7 (d, 8.1 Hz, 1H).
13C NMR (25oC, CDCl3) : δ (ppm) = 110.0, 123.6, 123.8, 123.9,
125.7, 126.9, 127.4, 128.2, 130.7, 134.9, 139.0.
Elemental analysis: found (%) C 86.7 (th: 87.0), H 5.89
(5.70), N 7.29 (7.30).

b) Synthesis of N- (naphthyl) -2- (dicyclohexylphosphino) -
pyrrole

1.6 ml (15 mmol.) of TMEDA are added to a solution of
1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution
(1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol.) is added
dropwise. After 3 hours' reflux (75°C), the colour has
changed from orange through green to black. Without
cooling, a solution of 2.2 ml (10 mmol.) of chlorodicyclo-
hexylphosphane in 20 ml of hexane is added dropwise and
refluxing is carried out for a further one hour. The colour
of the solution changes to yellow, and a white precipitate
forms. After cooling to RT, 3 0 ml of water are added to the
mixture. The aqueous phase is extracted 3 times using 20 ml
of hexane each time. The combined organic phases are washed
with 10 ml of water, dried over Na2SO4 and concentrated in
vacuo (45°C) . The orange oil that remains is refluxed for
30 minutes in 30 ml of MeOH (60°C) . On cooling to -25°C,
the product precipitates in the form of a yellow solid and
is filtered off (0.9 g, 24 %).
31P NMR (25°C, C6D6) : δ (ppm) = -23.3.


General procedure:
in a three nacked 100 ml round bottom flask with reflux
condenser, N-arylpyrrole (or N-arylindole or N-
arylimidazole) (10 mmol) was dissolved in 20 ml of freshly
distilled n-hexane under argon. TMEDA (15 mmol) was added
followed by n-BuLi (10 mmol, 1.6 M in hexane) at room
temperature. The reaction mixture was refluxed for 3 h. A
solution of the corresponding chlorophosphine (10 mmol in 5
ml hexane) was slowly added via syringe. The mixture was
further refluxed for lh. After cooling to room temperature,
degassed water (15 ml) was added and the mixture was
stirred to get a clear solution. The aqueous layer was
extracted with hexane <2x 15 ml) and the combined organxc

layers were washed with degassed water (15 ml) . The
solution was dried over Na2SO4 and concentrated at 45°C to
get a viscous liquid which was recrystallized from methanol
or toluene.

Example 66: Catalytic amination of aryl chlorides
A 30 mL pressure tube was loaded with Pd(OAc)2 (0.025
mmol), the ligand (0.050 mmol), NaOtBu (6.0 mmol) and was
purged by argon for 30 minutes. Then, were successively
added under argon, toluene (5 mL) , the aryl chloride (5
mmol) and the amine (6 mmol) . The mixture was stirred under
argon at 120 °C for 20 hours. After reaction, it was
diluted with di ethyl ether (15 mL) and washed with water (10
mL) . After extraction, the organic phase was dried over
MgSO4, concentrated under vacuum and the final product was
isolated by column chromatography (silicagel, hexane/ethyl
acetate 90/10). Alternatively, diethyleneglycol-di-n-
butylether or hexadecane was added as internal standard,
and quantitative analysis was done by gas chromatography.

WE CLAIM:
1. Process for the catalytic preparation of aryl olefins, dienes,
diaryls, benzoic acid derivatives, acrylic acid derivatives,
arylalkanes, alkynes, aryl ketones, carbonyl compounds or
amines from aryl halides or vinyl halides, characterized in that
catalysts containing at least one phosphane ligand of formula (I)
is used, the catalyst containing at least one palladium, nickel,
platinum, rhodium, iridium, ruthenium and cobalt atom or ion
as transition metal and the catalyst is a mono-, di-, tri- or tetra-
phosphane complex of the transition metal, wherein the catalyst
is either fed in the form of a complex compound to the reaction
mixture or is produced in situ by mixing at least one ligand of
formula (I) and at least one transition metal salt or transition
metal complex of a metal of sub-group VIII.
2. Process as claimed in claim 1, wherein the reaction is carried
out at temperatures of from 20 to 200°C.
3. Process as claimed in either claim 1 or claim 2, wherein the
phosphane ligand is used in excess relative to the transition
metal in a ratio of transition metal to ligand of from 1:1 to
1:1000.

4. Process as claimed in claim 3, wherein the ratio of transition
metal to ligand is from 1 to 1:100.
5. Process as claimed in any one of claims 1 to 4 the transition
metal is used in a ratio of from 5 mol.% to 0.001 mol. % relative
to the substrate.

Process for the catalytic preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives,
arylalkanes, alkynes, aryl ketones, carbonyl compounds or amines from aryl halides or vinyl halides, characterized in that catalysts containing at least one phosphane ligand of formula (I) is used, the catalyst containing at least one palladium, nickel, platinum, rhodium, iridium, ruthenium and cobalt atom or ion
as transition metal and the catalyst is a mono-, di-, tri- or tetra-phosphane complex of the transition metal, wherein the catalyst
is either fed in the form of a complex compound to the reaction mixture or is produced in situ by mixing at least one ligand of formula (I) and at least one transition metal salt or transition
metal complex of a metal of sub-group VIII.