Organometallics 1993,12, 2377-2379
2377
Exclusive Formation of cis-PhCH=CH(SiEts) by Addition of HSiEt3 to PhC-CH Catalyzed by R u H C ~ ( C O ) ( P I P ~ ~ ) ~ Miguel A. Esteruelas, Juana Herrero, and Luis A. 010. Departamento de Qutmica Inorgdnica, Instituto de Ciencia de Materiales de Aragbn, Universidad de Zaragoza, CSIC, 50009 Zaragoza, Spain Received January 6, 1993 Summary: RuHCl(CO)(RPr3)zis found to be very active and highly selective catalyst for the addition of triethylsilane to phenylacetylene. The reaction leads to cisPhCH-CH(SiEt3) with a selectivity of 100%. Although the vinyl compound Ru((E)-CH=CHPh)Cl(CO)(PiPr3)z is the main species under hydrosilylation conditions, the catalysis proceeds via the initial interaction of the catalyst with the silane.
Scheme I Ph-CSC-H
I
H Ci, R ,u P!Pr, !P~~P’ ’CO
la
Introduction Vinylsilanes have been shown to be versatile intermediates in organic synthesis.l They usually are prepared from olefins by catalytic dehydrogenative silylation2 or from alkynes by catalytic addition of silanes.3 Both processes lead to mixtures of trans- and cis-vinylsilanes. The hydrosilylation of terminal acetylenesgenerallytends to proceed thraugh cis addition, resulting in trans adducts as main products of the reactions. The complexes MHCl(CO)(PiPr3)2(M = Ru (la), Os ( 1b))in the presence of NaB& or KOH catalyzehydrogentransfer reactions from 2-propanol to cyclohexanone, acetophenone,’ benzylideneacetone? and phenylacetylene.6 Under a hydrogen atmosphere, they are very active homogeneous hydrogenation catalysts for styrene,’ cyclohexene,cyclohexadienes? phenylacetylene? diphenylacetylene! and benzylideneacetone.’J Recently, we have observedthat l b is also an active catalyst for the addition
A
w
prp’
H\/c-c\
Et3SI
’CO 2a
LE13
of triethylsilane to phenylacetylene.lO As a continuation of our work in this field, we now describe the addition of triethylsilane to phenylacetylene catalyzed by la. Results and Discussion
It was previously reported that the complexes la and l b react with phenylacetyleneto give the vinyl derivatives M((E)-CH=CHPh)Cl(CO)(PiPr3)2 (M = Ru (2a), Os (2b))11(eq 1).
M= RU (2r),OS (2b)
M= Ru (la),Os (lb)
(1)(a) Chan, T.H. Ace. Chem. Res. 1977,10,442. (b) Hudrlik, P. F. In New Applications of OrganometallicReagents in Organic Synthesie; Seyferth,D.,Fd.;Elaevier:Amsterdam, 1978;p 127. (c) Cook, F.;Moerck, R;Schwindaman,J.; Magnu, P. J. Org. Chem. 1980,45,1046. (2)Recentexamplea: ( a ) T d e , R . S.;Crabtree,R.H.Organometallics 1991,10,416. (b) O j i i , I.; Donovan, R. J.; Cloe, N. Organometallics 1991,10,2606.(c) Carey, J. Y.; Zhu, X. Organometallics 1992,11,672. (d) Yamamoto, K.; Tabei, T. J. Organomet. Chem. 1992,428,C1. (e) T~M.;Uchimara,Y.;Lautenechleger,H.J. Organomet.Chem. 1992, 428, 1. (0 Doyle, M. P.; Devora, G. A.; Nefedov, A 0.;High, K. G. Organometallics 1992, 11, 649. (e) Duckett, S. B.; Perutz, R. N. Organometallics 1992, 11, 90. (h) Kesti, M. R.; Waymouth, R. M. Organometallics 1992,11,1096. (3)(a) Chatani, N.;Takeyau, T.; Horiuchi, N.; Hanafuea, T. J. Org. Chem. 1986,53,3639. (b) Caseri, W.; Pregoein, P. 5. Organometallics 1986,7,1373. (c) Fernbndez, M. J.; Om,L. A.; Manzano,B.R. J. Mol. Catal. 1986, 46, 7. (d) Nagashima, H.;Tatebe, K.; Iehibhi, T.; SakaLibara, J.; Itoh, K. Organometallics 1989,8,2496.(e) Tenke, R.S.; Crabtree, R. H. J. Chem. SOC.,Chem. Commun. 1990,1066. (0Lewis, L.N.; Sy, K. G.; Bryant, F. L.; Donahue, P. E. Organometallics 1991,10, 3750. (e) Watmmbe, H.;Asami,M.;Nagai,Y.J. Orgonomet.Chem. 1980, 195,363. (h) Wada, F.;Abe,S.;Yonemaru, N.; Kikukawa,K.; Matauda, T. Bull. Chem. Soc. Jpn. 1991,64,1701. (i) Ojimn, I.; Cloa, N.; Donovan, R. J.; Ingallha, P.Organometallics 1990,9,3127.(j)Brady, K.A.; Nile, T.A J. Organomet Chem. 1981,206,299. (4) (a) Eetmwlae, M. A.; Sola, E.;Oro,L. A.; Werner, H.; Meyer, U. J. Mol. Catal. 1988,46,1. (b) Eeteruelae, M. A.; Valero, C.; Oro,L. A.; Meyer,U.; Werner, H. Znorg. Chem. 1991,30,1169. (6)Eaterueh, M. A; Sola, E.; Om,L. A.; Werner, H.; Meyer, U. J. Mol. Catal. 1989,63,43. (6)(a) Werner, H.; Meyer, U.;Eetarueh, M. A.; Sola, E.; Oro, L. A. J. Orgonomet. Chem. 1989,366,187. (b)Eepuelae, J.; Estarueh, M.A.; Lahm, F. J.; Om, L. A; Valero, C. Organometallics 1993,12,663. (7)Andrioh, A.; Eeteruelae, M. A,; Meyer, U.; 010,L. A; SAnchezDelgado, R. A.; Sola, E.; Valero, C.; Werner, H. J. Am. Chem. SOC.1989, 111,7431.
CkRu,PiPr3 H P H
We have now found that 2a reacts with triethylsilane to give la and trans-PhCH==CH(SiEt3)l2(eq 2).
2a H
la
The chemical transformations collected in eqs 1 (M = Ru) and 2 can be summarized in Scheme I, which shows a stoichiometric addition of triethylsilane to phenylacetylene in the presence of la. The elementarysteps involved (8) Eateruelaa, M. A.; Sola,E.;Oro,L.A.; Meyer, U.; Werner, H. Angew Chem., Znt. Ed. Engl. 1988,27,1563. (9)& b N e h , M. A.; Oro,L. A.; Valero, C. Organometallics 1992,11, 3362. (10)Eataruelaa, M. A.; Oro,L. A.; Valero, C. Organometallics 1991,10, 462. (11)Werner, H.;Eatmuelas, M. A.; Otto,H. Organometallics l986,5, 2296. (12)1H NMR in CDCls: d 7.40-7.16 (Ph), 6.82 (dd, PhCH-, J- * 19.36,1.00 Hz),6.34 (dd, 3cH(Sit& J ~ IH19.36,1.00 Hz),0.91 (t, SiCHzCHa, JH-H= 7.80 Hz), 0.68 (9, SiCH&Ha, JH-H = 7.80 Hz).
0276-733319312312-2377$04.00/0 0 1993 American Chemical Society
Notes
2378 Organometallics, Vol. 12, No.6, 1993
Scheme I1
in the reaction shown in eq 1are too rapid to be observed by spectroscopic methods. In order to obtain more information about the eventa involved in this process, we carried out the reaction of RuDCl(CO)(PiPra)z(la& with phenylacetylene. Addition of the stoichiometricamount of the alkyne to a benzene-de solution of la-dl contained in a NMR tube under argon yields 2a-dl (eq 3).
SiEt,
[MI,
ph/C=c
