Synthetic and mechanistic studies of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium(II) complexes

被引:143
作者
Widenhoefer, RA [1 ]
机构
[1] Duke Univ, PM Gross Chem Lab, Durham, NC 27708 USA
关键词
D O I
10.1021/ar010040n
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This Account describes the development and mechanistic study of the cycloisomerization and cyclization/hydrosilylation of functionalized dienes catalyzed by cationic palladium (II), complexes. These transformations are characterized by good functional group compatibility, high regio- and stereoselectivity, and low air- and moisture-sensitivity. Mechanistic studies of palladium phenanthroline-catalyzed diene cycloisomerization and cyclization/hydrosilylation established mechanisms involving C-C bond formation via intramolecular carbometalation of an alkyl olefin chelate complex, which was directly observed in the context of cyclization/hydrositylation.
引用
收藏
页码:905 / 913
页数:9
相关论文
共 49 条
[41]   PALLADIUM-CATALYZED CYCLOISOMERIZATIONS OF ENYNES AND RELATED REACTIONS [J].
TROST, BM .
ACCOUNTS OF CHEMICAL RESEARCH, 1990, 23 (02) :34-42
[42]   ATOM ECONOMY - A CHALLENGE FOR ORGANIC-SYNTHESIS - HOMOGENEOUS CATALYSIS LEADS THE WAY [J].
TROST, BM .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (03) :259-281
[43]   APPLICATION OF OLEFIN METATHESIS TO ORGANIC-SYNTHESIS - SYNTHESES OF CIVETONE AND MACROLIDES [J].
TSUJI, J ;
HASHIGUCHI, S .
TETRAHEDRON LETTERS, 1980, 21 (31) :2955-2958
[44]   Palladium-catalyzed ring-opening cyclization/hydrosilylation of 1-cyclopropyl-1,6-heptadienes to form (E)-1-butenyl cyclopentanes [J].
Wang, X ;
Stankovich, SZ ;
Widenhoefer, RA .
ORGANOMETALLICS, 2002, 21 (05) :901-905
[45]   Synthesis of carbobicyclic compounds via palladium-catalyzed cyclization/hydrosilylation: Evidence for reversible silylpalladation [J].
Wang, X ;
Chakrapani, H ;
Stengone, CN ;
Widenhoefer, RA .
JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (05) :1755-1760
[46]   Silane-promoted cycloisomerization of functionalized 1,6-dienes catalyzed by a cationic (π-allyl)palladium complex [J].
Widenhoefer, RA ;
Perch, NS .
ORGANIC LETTERS, 1999, 1 (07) :1103-1105
[47]   Cyclization/hydrosilylation of functionalized dienes catalyzed by a cationic palladium phenanthroline complex [J].
Widenhoefer, RA ;
Stengone, CN .
JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (23) :8681-8692
[48]   Tandem cyclization/hydrosilylation of functionalized 1,6-dienes catalyzed by a cationic palladium complex [J].
Widenhoefer, RA ;
DeCarli, MA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (15) :3805-3806
[49]   Ruthenium(II)-catalyzed isomer-selective cyclization of 1,6-dienes leading to exo-methylenecyclopentanes:: Unprecedented cycloisomerization mechanism involving ruthenacyclopentane(hydrido) intermediate [J].
Yamamoto, Y ;
Nakagai, Y ;
Ohkoshi, N ;
Itoh, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (26) :6372-6380