Hydrosilylation of alkynes mediated by N-heterocyclic carbene platinum(0) complexes

被引:107
作者
De Bo, G [1 ]
Berthon-Gelloz, G [1 ]
Tinant, B [1 ]
Markó, IE [1 ]
机构
[1] Catholic Univ Louvain, Dept Chim, B-1348 Louvain, Belgium
关键词
D O I
10.1021/om050866j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The hydrosilylation of terminal alkynes by silanes catalyzed by N-heterocyclic carbene platinum(O) complexes has been investigated. The alkynes included 1-octyne and phenylacetylene. The silanes investigated were bis(trimethylsilyloxy)methylsitane, (trimethylsilyloxy)dimethylsilane, tert-butyldimethylsilane, triphenylsilane, phenyldimethylsilane, triethylsilane, and triethoxysilane. X-ray crystal structures for [Pt(N,N'-dicyclohexylimidazol-2-ylidene)(eta(2)-dimethylacetylenedicarboxylate)(2)] (8) and [Pt{C(E)=C(E)-C(E)=C(E)}(N,N'-dimethylbenzimidazol-2-ylidene)(sigma-NCCH3)] (10) (E = CO2Me) have been obtained. A selectivity model, based on structural parameters of the N-heterocyclic carbene, has been devised in order to rationalize the observed regioselectivity obtained. By a judicious choice of catalyst, alkyne, and silane, the regioselectivity of the addition can be controlled.
引用
收藏
页码:1881 / 1890
页数:10
相关论文
共 87 条
[71]   Selective hydrosilylation of styrene using an in situ formed platinum(1,3-dimesityl-dihydroimidazol-2-ylidene) catalyst [J].
Sprengers, JW ;
Mars, MJ ;
Duin, MA ;
Cavell, KJ ;
Elsevier, CJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2003, 679 (02) :149-152
[72]   A mild preparation of vinyliodides from vinylsilanes [J].
Stamos, DP ;
Taylor, AG ;
Kishi, Y .
TETRAHEDRON LETTERS, 1996, 37 (48) :8647-8650
[73]   Insights into the origin of high activity and stability of catalysts derived from bulky, electron-rich monophosphinobiaryl ligands in the Pd-catalyzed C-N bond formation [J].
Strieter, ER ;
Blackmond, DG ;
Buchwald, SL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (46) :13978-13980
[74]   PREPARATION, STRUCTURE, AND ROLE OF TETRAKIS(METHOXYCARBONYL)PALLADIIACYCLOPENTADIENE CYCLIC DIOLEFIN COMPLEXES IN SELECTIVE PALLADIUM-CATALYZED CYCLOCOTRIMERIZATION OF ACETYLENES WITH OLEFINS [J].
SUZUKI, H ;
ITOH, K ;
ISHII, Y ;
SIMON, K ;
IBERS, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (26) :8494-8500
[75]  
TAKAHASHI K, 1993, TETRAHEDRON LETT, V34, P8263
[76]   A SELECTIVE SYNTHESIS OF (E)-VINYLSILANES BY CATIONIC RHODIUM COMPLEX-CATALYZED HYDROSILYLATION OF 1-ALKYNES AND TANDEM HYDROSILYLATION ISOMERIZATION REACTION OF PROPARGYLIC ALCOHOLS TO BETA-SILYL KETONES [J].
TAKEUCHI, R ;
NITTA, S ;
WATANABE, D .
JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (10) :3045-3051
[77]   SILAFUNCTIONAL COMPOUNDS IN ORGANIC-SYNTHESIS .21. HYDROGEN-PEROXIDE OXIDATION OF ALKENYL(ALKOXY)SILANES [J].
TAMAO, K ;
KUMADA, M ;
MAEDA, K .
TETRAHEDRON LETTERS, 1984, 25 (03) :321-324
[78]   SILAFUNCTIONAL COMPOUNDS IN ORGANIC-SYNTHESIS .32. STEREOSELECTIVE HALOGENOLYSIS OF ALKENYLSILANES - STEREOCHEMICAL DEPENDENCE ON THE COORDINATION STATE OF THE LEAVING SILYL GROUPS [J].
TAMAO, K ;
AKITA, M ;
MAEDA, K ;
KUMADA, M .
JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (06) :1100-1106
[79]   STERIC EFFECTS OF PHOSPHORUS LIGANDS IN ORGANOMETALLIC CHEMISTRY AND HOMOGENEOUS CATALYSIS [J].
TOLMAN, CA .
CHEMICAL REVIEWS, 1977, 77 (03) :313-348
[80]   THE ATOM ECONOMY - A SEARCH FOR SYNTHETIC EFFICIENCY [J].
TROST, BM .
SCIENCE, 1991, 254 (5037) :1471-1477