CA1318918C

CA1318918C - Codimerization of an olefin

Info

Publication number: CA1318918C
Application number: CA000616182A
Authority: CA
Inventors: Gunther Wilke; Jaroslaw Monkiewicz; Herbert Kuhn
Original assignee: Studiengesellschaft Kohle gGmbH
Current assignee: Studiengesellschaft Kohle gGmbH
Priority date: 1986-05-30
Filing date: 1991-09-26
Publication date: 1993-06-08
Anticipated expiration: 2007-05-28
Also published as: US4912274A; JPH0867642A; EP0247595B1; CA1301771C; JPH0822867B2; IE60201B1; EP0247595A3; DK277787D0; EP0247595A2; DE3775621D1; DK277787A; US4900866A; IE871426L; JP2686427B2; CA1318919C; CA1318920C; US4827067A; DE3618169A1; ATE71102T1; ES2027654T3

Abstract

CODIMERIZATION OF AN OLEFIN

ABSTRACT

In the codimerization of an olefin employing a .pi.-allylnickel compound as a catalyst, the improvement which comprises employing the .pi.-allylnickel compound in the form of a complex with bis-(3R)-3-((1R,5R,8R)-5,9,9-trimethyl-4-[(1R)-1-phenylethyl]-4-aza-5-phosphatricyclo-[6.1.11.8.02.6]-dec-2(6)-enyl).

Description

~3~8~ ~

Xt has been known that olefins can be dimerized or co-dimerized by means o~ nickel-contalning and phosphane-modified catalyets. Thus, the co-dimer-ization of cycli~ dienes or stra~ned olefins such as norbornene and ethene by using ~-allylnickel hal:ides or nickel(O) compounds and the activation thereof by means of Lewis acids and the modification with acyclic phosphanes, also optically active acyclic phosphanes, have been described several times LGerman Patent 20 39 125, Studiengesellscha~t Kohle mbH. (priority lg70); U.S. patent 3,978,147,~Studiengesellschaft Kohle mbH. ~priority 1~73); ~.S. patent ~,09~,834, Studien-gesell~chaft Kohle mbH. (priority ls76); G. Wilke et al., Angew. Chem. I972, 1070; B. Bogdanovic et al., Angew. Chem. 1973, 1013; F. Petit et al., Bull. Soc.
Chim. 1979, II-415; 3. Chem. Soc. 1980, 937; G. Buono et al., J. Org, Chem. 1985, 50, 178~J. The processes known 80 far ha~e technisal disadvantages, as the catalysts show only relatively low activities and moreoverj the accomplished selectivities are in-~u~ficient. The maximum numbers of catalytic cycles attainable with the processes described so far are too low for a commercial use.
'~' :~ 3 ~

Surprisingly, it was now found that said technical defects of the processes known so Par can be o~ercome ~y using azaphospholenes as modifying ligands, ~he substituQnts of which azaphospholenes, due to their spatlal raquirements, will block c:erta~n rotations in the catalyst complexes. Therefrom ensue relatively rigid arrangements at the catalyst wherein always one nickel atom is complexed to each phosphorus atom. Such ligands are phospholenes having the followlng structu-re-' 1/

wherein the moieties Rl and R2 may be alkyl, aryl andaralkyl groups which may be varied within wide limits.
Upon the pre~erred selection of Rl = -CH-C6H5, preferably in the optical ~- or S-form~, respectively, and R2 = CH3, particularly good results are obtained.
The up to now unknown diastereomer built up with these substituents has the ~ollowing structure and con-~iguration according to x-ray structural analysis:

f~

C

Ci~ C~l C-7 ),~ CJ~
~4~ Jc~5 This diastereomer 6a was obtained by th~ ~ollowing route ~tarting from (-)--pin~ne or [(-)-(lR,5S~-myrtenal 1] and (~)-R-a-phenylethylamine 2.

~ I f ~ ~ ~ U~ N ~
2 h~ ~~

.

3 ~ he,P~ , t ,~p,~
3 t4 4 . ~.J ~- ~J e.

~t ~ 4b -~ ~, 3 ~ ~ 9 ~ ~

* rP~
~ 4 $
4~4b -lO '~ to ro~n ' t~ature ~ b In an analogous manner, starting from (~-a-pinene ~nd (-)-S-a-phenylethylamine there may be prepared the compound 6a' which is the enantiomer o~ thP afore-mentioned diastQreomer. 6a and 6a' as ligands in nic~el-containing catalysts have the effect that, e.g., the co-dimerization of norbornene with ethene may be realized even at a temperature of from +60 C to -120 ~C, and preferably of from -20 C to -B0 C, with an activity of 20,000 cycles per hour and selectivities of ~90%. The (-)-exo-vinylnorbornane formed according to the following reaction equation + C2U~ catalyst> ~C=~

by the use o~ 6a as ligand in the nickel catalyst in CH2C12 has an ~nantiomeric excess (e.e.~ o~ 57~, ~.e.
the ligand ~a causes not only high activity and selec~ivity, but also a high optical induction, so that according to the process an optically active product is obtained 78.5% of which consist of on enantiomer.

If, ~ontrary thereto, an analogous phospholene is built up starting from (-)-a-pinene and (-) S-a-phenylethy].amine, then another diastereomer 6b results L 3 ~

therefrom, the structure of which was also elucidated by X-ray analysis.

C,~'.' '~C:I. ' ~C

6b, as a catalyst component shows the ef~ects as indicated above for 6a with respe~t to catalyst activity to a degree reduced by the factor 100~ i.e.
under the same conditions there are accomplished about ~00 cycles instead of 20,000 cycles. Then the obtained product shows (+) rotation and is (~)-exo-vinylnor-bornane with an e.e. of 40%. Molecular modslling investigations on 6a and 6b show that in ~a rotat~ons around certain bonds, e.g. the central C-C bond (Cl -C30) are largely restricted, while this is not the case in 6b. In 6a therefrom result ~he rigid arrangements as mentioned which correspond to secondary structures in enzymes.

Synthesis of A~aphospholene (lR,5$)-6,6-Dimethyl 2-[(lR)-l-N-phenylethylaza~
methino]bicyclo~3.1.1]hept~-2~ene 3 34.37 g (0.284 mol~ of (~)-(lR)-phenylethylamine 2 are charged in a 250 ml flask andL heated to 70-80 C.
At this kemperature 42~94 g (0.286 mol~ of (-)-(lR,5S)-myrtenal 1 are dropwise addsd wlthin 1 h. A two-phase mixture is formed stirring of ~hich is continued ~or 1 h. ~fter cooling to room temperature 50 ml o~ ether are added, the aqueous phase is separated (4 ml), and the organic phase is dried with KOH/Na~SO4. Then tha ether is condensed off, and th~ crud~ product 3 is distilled under high vacuum.
Yield: 62.3 g (86.7~ of theory); b.p. 108-112 C.

5-Bromo-5,9,9-trimethyl-4-~lR)-l-phenylethyl]~4-aza-5-~4-phosphoniatricyclo ~6.1.11 ~.02'~]-dec-2(3)-ene bromide 4a, 5-Bromo-5,9,9-trimethyl-4-t(lR~ ph~nylethyl]-4-aza-5 ~4-phosphoniatricysl~-~6.1.11 8.0~ 6]-dec-2t6~-ene bromide 4b 49.40 g ~0.195 mol) of the azadiene 3 in 700 ml of n-pentane are charged, and 40.14 g (0.195 mol) of MePBr2 in about 200 ml of n-pentane are dropwise added.
A yellow preGipitate is immediately ~ormed. A~ter the MePBr2 addition, the reaction mixturP is stirred for 4 days. Then:the yell~w solid (cruds phosphonium salts 4) are filtered off, washed three times wi~h 100 ml o~
n-pentane each and dried in vaauo.
Yield of crude material: 75.1 g (84.0~ of theory).
~) 31p_NMR 4a 77~2 ppm (CD2C12~; ~k 67-1 ppm ( CD2C12 ) -" ~ 3 ~ $ ~ ~ ~
~ 7 -Bis-~3R)-3-((lR,5R,8R3-5,9,9-trimethyl-4-[(lR)-l-phenylethyl]-4-a~a~5-phosphatricyclo-~6.1.11 8.o2 6]-dec-2(6)~enyl} 6a 10.05 g ~21.9 mmol) oP the orude product 4 are suspended in 100 ml of THF on a ~:rit, the ~iltrate is sollected in a flask, and the resiclue is discarded. To the orange-colored filtrate there are added at 10 C
0.66 g (272 mmo}) of active magnesium portionwise under vigorous stirring. After the completion of the additlon the batch is allowed to warm up slowly to room temperature and is stirred oYernight. A~t~r the solvent has been condensed off, 200 ml of ether are added to the residue, and the mixture is filtered. The ether is condensed off from the yellow filtrate to obtain 10.62 g of a viscous residue which is dissolved in 4 to 5 parts by volume of methanol with heating to about 60 C0 In a water bat~ (about 60 C) the mixture is stirred and allowed to cool to room temperature overnîght~ A colorless precipitate of 6a is formed.
Yield: 0~84 g (12.9~ of theory); m.p. 134-135 C
(recrystallized from ethanol).
~) 31p_NMR: 49.9 ppm (toluene); Ea~589 = -64.69 (0.64 g~100 ml of CH2C12).

The azaphospholenes of the type 6a are suitable ~or the preparation o~ catalysts o~ a highly selective activity which in turn are capable o~ converting un-saturated hydrocarbons into optically active compounds.
Thus, an optically active vinyl bicycloheptane is obtained from bicycloheptene and ethylene in space-time yields not yet described so ~ar. Said optically active vinyl bicycloheptane in turn may be the starting material ~ox the terpolymerization together with, e.g., -- 8 ~

ethylene and propylene to give polymers, and more part-icularly optically active polymers. Optically active polymers~ due to their high sterical regularity, have ~mproved physical and mechanical properties. Thu~, optically active polymers are suitable as absorben~s for the separation of enantiomers. In the zame manner, an optically active 3-phenylbut~3ne-l is selectively obtainable in high yield from styrene and ethylene by co-dimerization, and so are substituted 3-phenyl-butenes-l from substituted styrenes and ethylene. The polymer~zation of this a-ole~in products to optically active polymers ls effected in the same way as the terpolymerization set forth above.

A further application of the azaphospholenes in the form of the described complex compounds together with organoaluminum compounds is the selective change of the structure of, e.g., heptadiene-1,6 to form l-methyl-2-methylidene cyclopentene, as well as the co-dimerization o~ 1,3-cyclopentadiene and ethylene leading to op ically active 3-phenylpentens-1.

Catal tic Synthesis of Vinyl Bicycloheptane ~ .

Example 1 A 2-1 ~our~neck ~lask equipped with stirrer, drop-ping unnel and a Claisen head with thermometer is evacuated with heating and filled with argon. The flask is charged with 600 ml of CH2C12, and the drop-ping funnel is filled with 600 ml o~ a CH2C12 solution of 400 g (4.25 mol) bicyclo~2.2.1]heptene. The flask is cooled to -65 C while ~ts co~tsnt is stirred, and 0,047 g (0.108 mmol) o~ ~ allylnickel chloride/phospha-ne 6a complex ~Ni:P - 1:1) dissolved in about 10 ml o~

1318 ~ ~?j cooled CH2C12 and 0,239 ml (1 mmol) of Et3A12C13 ~P:Ni:Al = 1:1:20) are added, whereupon the complex solutlon becomes violet in color. After brie~ly evacuating with an oil pump, the vacuum is removed with dry ethylene, and th2 solution of bicycloheptene iB
dropwise added with stirring within 6 0 minutes. In the course thereof a high heat evolution is observed.
During the reaction period (90 minutes) ethylene is introduced into the apparatus whereby the reaction temperature is increased to -58 C.

Then the reaction is terminated by introducing gaseous ammonia, and the proAuct is condensed o~f ln vacuo. From the conden~ate thus obtained the solvent is distilled off under normal pressure, and the residue is distilled through a Vlgreux column.
Yield: 384 g (74% of theory).
~ exo-2-vinyl bicyclo[2.2.1]heptane (54% e.e.);
conversion number: 29,140.
t2]maX = (+) 51 : b.p. 54 QC/30 mbar:
D = 0.8726 g/cm .

Exampla 2 The procedure is a~ in Example 1, using a 0.5-1 four-neck flask. The flask is charged with 150 ml of CH2C12, and the dropping funnel is filled with 30 ml (0.32 mol) of bicyclot2,2.1]heptene in 50 ml of CH2C12.
The solvent i5 cooled to -70 C, and 0.0961 g S0.352 mmol) o~ bis-cyclooctadienenickel and 0.105 g (O.352 mmol) of the phosphane 6a are added. The reaction mixture is allowed to warm up slowly to -15 C/ until a strongly yellow clear solution is formed, and then is again cooled to -70 C, and 0.080 ml ~0.352 mmol~ of Et3A12C13 (P:Nl:Al = 1:1:2) 1 3 ~ 3 are addPd. After renewed heating to -20 C the solution is saturated with ethylene , and the solution of bicycloheptene is dropwise added within 15 minukes.
The reaction mixture i5 kept saturated with ethylene by vigorous stirring ~or 60 minutasS The reaction is terminated with gaseous ammonia. The product is condensed off, the solvent is withdrawn, and the residuP ls distilled through a Vigreux column about 30 cm in length.
Yield: 35 g (90% o~ theory~.
~ exo-2-vinyl bicyclo~2.2.1]heptanQ (8.2% e.e.);
conversion number: 815.

Example 3 ~ he proce~ure i~ as in Exampla lo A l-liter ~lask i8 charged with 500 ml of chlorobenzene, and the drop-ping funnel is filled wi~h 30 g (0.32 mol) of bicyclo-heptene in 50 ml of chlorobenzene. The chlorobenzene is stirred and cooled to -40 C, and 0.090 g (0.186 mmol3 of ~-allylnickel/phosphane-6a complex in a~out 15 ml of cooled chlorobenzene and 0.135 g ~1.12 mmol) of Et2AlCl (P:Ni:Al ~ 6) are added thereto. Then the solution of bicycloheptene is drop-wise added within about 15 minutes, and ethylene is introduced into the apparatus. In the course of 2 h the reaction mixture is heated to +40 C.

The catalysis is terminated by introducing gaseous ammonia, and the produ~t is condensed off in vacuo.
From the condensate thus obta~ned the solvent is distilled off under normal pressure, and the residue is distilled through a Vigreux column.
Yield: 34 g (87.5% of theory).
(+)-exo-2-vinyl bicycloE2.2.1]heptane (10.8% e.e.);

11 3~

conversion nun~er: 1498. Thus, in chlorobenzene the formation of the (~-form is prPferred.

Example 4 The procedure iæ as in Example 1. A 0.5-1 flask is charged with 150 ml of CHCl~, and the dropping funnel is filled with 30 g ~0.32 mol) of bicyclo-heptene in 50 ml of C~C13. The ~olvent is cooled to -30 C, and 0.020 g t0.114 mmol) oP nickel acetate and 0.0678 g (0~228 mmol) of phosphane 6a are added. The reaction mixture is stirred for 30 minutes at -30 C, and then 0.133 g (0.684 mmol) of AgBF4 (P:Ni:BF~ =
2:1:6) ara added. After stirring ~or another 30 minutes the solution of bicycloheptene is dropwise added within 10 mi~utes, and e~hylene is simultaneously lntroduced into the apparatus. After 60 minutes the reaction is terminated by introducing gaseous ammonia.
The product is condensed oPf, the solvent is withdrawn, and the residue is distilled.
Yield: 32 g (85~ of theory).
(-)-exo-2-vinyl bicyclo~2.2.1]heptane (29~ e.e.);
conversion number: 230Q.

Example 5 The procedure is as in Example 1. A 0.5-1 flask is charged with 150 ml of CH2C12, and the dropping ~unnel is ~illed with 15 g (0.16 mol) of bicyclo-heptene. The solvent is stirred and cooled to -72 C, and 0.287 g (0.66 mmol) of ~-allylnickel/phosphane-6b complex in about 20 ml o~ cooled CH2C12 and 0.150 ml (0-66 mmol) of Et3A12C13 (P:Ni:Al ~ 2) are added thereto, whereby the complex solution becomes vlolet in color. Then at -72 C the solution of bicycloheptene - ~ 3 ~

is dropwise added within 30 minutes, and ethylene is simultaneously introduced into t:he solution. Upon completion of the bicycloheptlene addition, the introduction of ethy}ene is continued for another 30 min. The reaction is terminated by .1ntroducing gaseous ammonia, and the product is condensed off in vacuo, the solvent i5 withdrawn, and the residue is distilled.
Yield: 18 g (92% of theory).
(+~ exo-2-vinyl bicyclo[2.2.1~heptane (38% e.e.);
conversion number: 224.

Example 6 The procedure is as in Example 1. A 0.5-:l flask is charged with 150 ml of C~2C12, and the dropping funnel is filled with 18 g (0.19 mol) of bicyclo-heptene in 20 ml o~ CH2C12. The solven~ is Gtirred and cooled to -30 ~, and 0.283 g ~0.946 mmol3 o~ tha mixture of the phosphane isomers 5a and 5b and 0.128 g (0.473 mmol) of bis-~-allylnickel chloride are added.
The reaction mixture is stirred for 30 minutes and then cooled to ~70 DC, and 0.454 ml (1.892 mmol) of Et3A12C13 (P:Ni:Al = 1:1:4~ are added thereto. A~er briefly evacuating with an oil pump, the vacuum is removed with dry ethylene, and the solution o~ bicyclo-heptene i6 dropwise added within 15 minutes. Then the introduction o~ ethylene into the apparatus is con-tinued for another 15 min. The reaction is terminated by introducing gaseous ammonia, the product is con-densed off in vacuo~ the ~olvent is withdrawn, and the __ residue is distilled.
Yield: 6 g (26% of theory).
~ exo-2~vinyl bicyclot2.2.1]heptane (3.4~ e.e.)t conversion number: 52.

Example 7 The procedure is as in Example 1. A 0.5-1 ~lask is charged with lS0 ml of CH2C12, and the dropping funnel i8 filled with 30 g (0.32 mol) o~ bicyclo-Aeptene in 50 ml of CH2C12. Th~ solvent is cooled to -65 C, and 0.086 g (0.197 mmol~ of ~-allylnickel chloride/phosphane-6a complex dis~solved in 10 ml o~
cooled CH2C12 ~nd 0.227 ml o* Et3A12C13 are added. The reaction mixture ist stirred at -65 C ~or 15 minutes.
Then 0.118 g (0.394 mmol~ of the phosphane 6a ~P:Ni:Al = 3:1:10) are added, and the solution is stirred for another 10 minutes. Then th~ solution o~ hicyclo-heptene is dropwise added within 15 minutes, and ethylene is simultaneously introduced into the appara-tus. The reaction is terminated by introducing gaseous ammonia, the product i5 condensed off ln vacuo, tha solvent is withdrawn, and the residue is di~tilled.
Yield: 34 g (87% of theory).
~ exo-2-vinyl bicyclo[2.2.1]heptane ~57% e.e.);
: conversion number: 1413.

: Example 8 A 100-1 ~lass reaction vessel equipped with stirrer, a 25-1 ~eed tank and an in~ernal thermometer is provided with an argon atmosphere. The react~on vessel is charged with 50 1 of CH2C12, and the feed tank is ~illed with 10.13 kg (107.7 mol) of bicyclo-heptene in 10 1 of CH2Cl~. The charged solvent is cooled to -40 C by means of a refrigerating machine, and the bicycloheptene solution is cooled to -13 C.

Then ethylene is lntroduced, and 23 ml (0.102 mol~
of Et3A12C.13 and 4.448 g ~0.0127 mol) o~ ~-allylnickel - ~ 3~

chlorlde/phosphane-6a complex dissolved in ~0 ml of CH2C12 (P:Ni:Al = 1:1:20) are added. Then, with simultaneous introduction uf ethylene, the solution of bicycloheptene i8 allowad to run in wlthin 6 hour~.
With ~ull output of the connected ~efrigerating machine the reaction temperature increases to -31 C. Afker 6.5 h the reaction i~ terminated by the introduction o~
gaseou~ ammonlaO Then ths solver~t is distilled off under normal pressure, and the residue is fractioned through a column.
Yield: 8.0 kg (65.6 mol; 60.9% of theory~
~ exo-2-Yinyl bicyclo~2.2.1]heptane (32.6% e.e.);
conver~ion number: 6388.

Catalytic Synthesis of OPtically _Active 3-Phenyl-butene-l Example 9 A 2-1 four-neck ~lask eguipped with stirrer, drop-ping funnel and a ~laisen head with thermometer is evacuated with heating and filled with argon. ~he flask is charged with 700 ml of CH~C12, and the drop-ping funnel is ~illed with 4~0 ml of a CH2C12 solution cooled to -30 ~C o~ 275 g (~.65 mol) of styrene. The flask is cooled t~ -70 DC while its content is stirred, and 0.590 g (1.3S mmol) of ~-allylnickel chloridefphos-phane 6a complex (Ni:P = 1:1) dissolved in about 15 ml o~ cooled CH2C12 and 0.70 ml (3.0 mmol) of ~t3A12C13 (P:Ni:Al = 1:1:3) are added. A~ter briefly evacuating with an oil pump, the vacuum i5 removed with dry ethylene, and the solut~on of styrene is dropwise added with stirring within 45 minutes. In the course thereof the solution becomes warmed up to -60 5C~ During the ~ 3 ~ iJ

reaction period (150 minutes) ethylene is introduced into the apparatus. The catalys:Ls is terminated by introducing gaseous ammonia, and the product is conden~ed off _ vacuo. From l:he condensate thus obtained the solvent i~ distilled off under normal pressure~ and the residue is distill2d through a Vigreux column. Yleld- 340 g (97~ of theory).
~ (R~-3-phenylbutene-1 (93% e.e.);
conversion number: lB90.
xample 10 The procedure is as in Example 1, using a 0.5-1 four neck ~lask. The flask is charged with 150 ml o~
CH2~12, and the droppiny funnel is filled with 18 g tO.17 mol) of styrene in 30 ml of CH2C12. The solvent is cooled to -70 C, and Q.0553 g (0.13 mmol) of ~-allylnickel chloride/phosphane 6a complex in about 15 ml of cooled CH2C12 and 0.030 ml (0.13 mmol) o~
Et3A12C13 are added, Thereafter the reaction mixture is warmed up to 0 C within 60 minutes. ~t 0 C ~he solution of styrene is dropwise added within 15 minutes, and ethylene is introduced into the apparatus.
The reaction i~ terminated by introduci~g gaseous ammonla, and the product ls condensad off in vacuo.
Then, the solvent is withdrawn, and the re~idue is distilled. Yield: 20.9 g (93% of theory).
~ (R)-3-phenylbutene-1 (76% e.e.);
converston number: 1216.
Example 11 The procedure is as in Example 1, usin~ a 0.5-1 four-neck ~lask. The flask ~ charged with 150 ml o~
toluene, and the dropping gunnel is ~illed with 20 g ~3~3~

(Ool9 mol) of styrene in 40 ml of toluene. At room temperature 0.120 g ~0.44 mmol) of bis cyclooctadiene-nickel and 0.131 g (0.4~ mmol) of the phosphane 6a are added. The reaction mixture is st.irred for 30 minutes, and then 0.106 g (0~8 mmol) o~ Et2AlCl (P:Ni:Al =
~ 43 are added. Then the solution o~ styrPne is dropwise added within 30 minute~3, and ethylene i~
introduced into the apparatus. By way o~ vigorous stirring the reaction mixture i9 kept saturated with ethylene ~or 4 hours. The catalysis is terminated by the addition of ethanol, and the product i3 condensed off in vacuo. From the condensate the solvent is distilled off through a Vigreux column under normal pressure, and the residue ls fractionated under vac~um.
Yield: 15.1 g (60.2% of theory~.
~ (R)-~-phenylbutene-l (53% e.e.);
con~ersion numher: 260.

Example 12 The procedure is as in Exampla 1. A 0.5-1 flask is charged with 15~ ml of CH2C12, and the dropping funnel is fllled with 20.3 g (0.195 mol) o~ styrene in 20 ml of CH2C12. The solvent is cooled to -60 C with stirring, and 0.0529 g (0.122 mmol) of ~-allylnickel bromide/phosphane 6a in 20 ml of cooled CH2C12 and 0-028 ml (0-122 mmol) of Et3A12C13 ~P:Ni:Al = 1:1:2~
are added. After warming up to room temperature (+22 C) the catalyst solution is saturated with ethylene, and the solution of styrene is dropwise added withln 15 minutes. The reaction mixture is kept in contact with ethylene by vigorous stirring for 30 minutes. Then the reaction is terminated by intro-ducing gaseous ammonia, and the product is condensed off in vacuo. From the condensate thus obtained the golvent i5 withdrawn, and the residue is distilled.

d~ J

Yield: 24.7 g (96~ of theory).
(+)-(S3-3-phenylbutene-1 (70% e.e.~, conversion number: 1533.

Example 13 The procedure is as in Example 1. A 0.5-1 flask is charged with 150 ml of CH2C12, and the dropp~ng funnel is filled with 20 g ~0.196 mol) of styrene in about 30 ml of CH2C12. The ~olvent is cooled to -30 ~C, and 0.050 g (0.286 mmol) of nickel acetate and O.0~6 g ~0.286 mmol) of phosphane 6a are added. The reaction mixture i~ stirred at -30 C for 60 minutes, and then Or222 g (1.144 mmol) of AgBF~ are added (P:Ni:BF4 = l l ~)o A~t~r another 30 minutes of stirring the solution of styrene is dropwise added within 20 minutes, and ethylene is simultaneously introduced into the apparatus. After 60 minutes the reaction is terminated by introducing gaseous ammonia, the product is condensed off in vacuo, the solvent is withdrawn, and the residue is distilled through a Yigreux colu~O
Yield: 12 g (46~ of theory).
~ (R)-3-phenylbutene-1 ~75~ e~e.~, conversion number: 317.

Catalytic_Synthesis of_ Optically Active l-Meth~1-2-methylidenecyclopentene Example 14 The procedure is as in Example 1 using a 0.5-1 four-neck flask. ~he ~lask is charged with about 150 ml of CH2C12~ and the dropping funnel is ~illed with 10 g (0.104 mol~ of heptadiene~ in about 20 ml o~ CH2C12. The solv~nt is cooled to -30 C, and - 18 - ~3~ 8 3 o.079 g (0.182 mmol) of ~-allylnickel chloride/phospha-ne 6a complex in 15 ml of cooled CH2C12 and 0.045 ml (0.197 mmol) of Et3A12C13 are added. Th2 solution becomes orange ln color. The catalyst mixtur~ is skirred at ~30 C for 30 minutes, and then the solution of hepkadiene-1,6 i~ dropwise added within 15 minutPs.
After 3 hours at -30 C the reaction is ~topped with gaseous ammonia, ~he crude product is condensed off in vacuo, the solvent ~ withdrawn, and the xesidue is distilled through a Vigreux column.
Yield: 9.4 g ~94% of theory).
~(S)-(~ methyl-2-methylidenecyclopentene/
b4p. 96 C: ~a]22 +61.6~ (undiluted3 ~93 % e.e.);
conversion number: 1540 ExamPle 15 A 100 1 glass reaction vessel equipped with stirrer, a 25-1 feed tank and an internal thermom~ter is provided with an argon atmosphere. The reaction vessel is charged with 40 1 of CH2C12, and the feed tank is filled with 8.26 kg ~79.5 mol) o~ styrene cooled to -20 ~C in 16 1 of CH2C12~ The charged solvent is cooled to -62 C by means of a refrigerating machine. The liquid is stirred, while 20.3 g (0.047 mol) of ~-allylnickel chloride/phosphane 6a complex dissolved in 100 ml of CH2C12 cooled to -60 C
and 25 ml ~0.109 mol) of Et3A12C13 (P:Ni:Al ~ 4.6) are added. Then ethylene is introduced, and the solution of styrene cooled to -20 ~C by mean~ of a second refrigerating machine is allowed to run in within 6 hours. The reaction temperature is maintained within a range Qf from -60 C to ~65 C. After 7 hours the reaction is terminated by the introduction of gaseous ammonia. The solvent is distilled off under 1 31$~

normal pressure~ and the residue is ~ractioned through a column.
Yield: 4.3 kg ~32.5 mol; 41% of theory; 87.4% e.e.).
(R)-3-phenylbutene-lt conversion number: 691.

Exam~le 16 The procedure is as in Example 1. A 0.5-1 flask is charged with 150 ml of CH2C12, and the dropping ~unnel is filled with 10 g (0.085 mol) of 4-methyl styrene in about 40 ml o~ CH2C12. The solvent is cooled to -70 C with stirring, and 0.109 g ~0.~5 mmol) of ~-allylnickel/phosphane 6a complex in about 20 ml of CH2C12 and 0.115 ml (0.50 mmol) of Et3A12C13 ~P:Ni:A1 = 1:1:4) are added. ~t -70 'C the solution of 4-methylstyrene is dropwise added within 15 minutes, and ethylene is simultaneously introduced into the solut~on. The reaction ~ terminated by introducing gaseous ammonia, and the reaction mixtura i~ condensed off in vacuo. The solvent ~s withdrawn, and the re-~idue is distilled in vacuo.
Yield: 11.7 g (94.4% of theory).
~ (R)-p-tolylbutene-l);
conversion number: 320; ~a]D2 ~9.89 in substance (95.2 % e.e.~.

Example 17 The procedure is as in Example 1. A 0.5-1 flask is charged with 150 ml of CH2C12~ and the dropping funnel is ~illed with 16 g ~0.242 mol) of monomeric cylopentadiene-1.3 in 15 ml of cooled CH2C12. The ~olvent iB cooled to -70 C, and 1.22 g ~2.81 mmol) of ~;allylnickel/phosphane 6a complex in 25 ml of aooled CH2C12 and 0.353 ml (2.81 mmol) ~ Et2AlCl are added -` 1 3 1 8 9 3~3 (P:Ni:Al = 1:1:1) . The reactiQn mixture is stirred at -70 C for 30 minute~. Then ethylene is introduced into the apparatus for 1 minute, ~nd then the solution o~ cyclopentadiene-1,3 is slowly aldded dropwise with simultaneous introduction o~ ethylene. ~he addition o~
the cyclopentadiene-1,3 601ution takes 1 hour. Then the reaction mixture was stirrend ~or another houx. The reaction is terminated ~y introdu~ing gaseous ammonia, and the product is condensed o~f in vacuo. The solvent i withdrawn, and the residue is distilled.
Yield: 8 g (0.084 mol: 35% of theory).
~ R)-3-vinylpentene-1 (92% e.e.);
conversion number: 30.

This is a divisional of application serial No. 538,306 filed May 28, 1987.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In the codimerization of an olefin employing a .pi.-allylnickel compound as a catalyst, the improvement which comprises employing the .pi.-allylnickel compound in the form of a complex with bis-(3R)-3-((1R,5R,8R)-5,9,9-trimethyl-4-[(1R)-1-phenylethyl]-4-aza-5-phosphatricyclo-[6.1.11 8.02.6]-dec-2(6)-enyl).

2. A codimerization according to claim 1 , wherein the olefin is a styrene.

3. A codimerization according to claim 2, wherein the styrene is a benzostyrene.

4. A codimerization according to claim 3, wherein the benzostyrene is 2-methoxy-6-vinyl-naphthalene.

5. A codimerization according to claim 1, wherein the olefin is an alkyl styrene.

6. A codimerization according to claim 5, wherein the alkyl styrene is 4-isobutylstyrene.