Silylene transfer to carbonyl compounds and subsequent Ireland-Claisen rearrangements to control formation of quaternary carbon stereocenters

被引:62
作者
Calad, SA [1 ]
Woerpel, KA [1 ]
机构
[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92627 USA
关键词
D O I
10.1021/ja042893r
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this communication, we demonstrate that silylene transfer to carbonyl compounds provides a new method for regio- and stereoselective enolate formation. Silylene transfer to a range of α,β-unsaturated esters under silver-catalyzed conditions proved to be a general method for the formation of oxasilacyclopentenes containing a cyclic silyl ketene acetal functionality. These oxasilacyclopentenes are useful synthetic intermediates that can undergo facile and selective Ireland-Claisen rearrangements and aldol addition reactions to provide products with multiple contiguous stereocenters and quaternary carbon centers. Copyright © 2005 American Chemical Society.
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页码:2046 / 2047
页数:2
相关论文
共 36 条
[1]   Reactions of α,β-enones with diazo compounds part 3 on the nature of the 1,5-ring closure of α,β-enone ylides [J].
Anaç, O ;
Özdemir, AD ;
Sezer, Ö .
HELVETICA CHIMICA ACTA, 2003, 86 (02) :290-298
[2]   CHEMISTRY OF OXASILACYCLOPROPANE .2. FORMATIONS OF DIOXASILACYCLOPENTANES IN REACTION OF OXASILACYCLOPROPANE DERIVATIVES WITH ADAMANTANONE AND NORBORNONE [J].
ANDO, W ;
IKENO, M ;
SEKIGUCHI, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (11) :3613-3615
[3]   OXASILACYCLOPROPANE - ISOLATION AND CHARACTERIZATION [J].
ANDO, W ;
HAMADA, Y ;
SEKIGUCHI, A ;
UENO, K .
TETRAHEDRON LETTERS, 1982, 23 (50) :5323-5326
[4]   SILACARBONYL AND SILATHIOCARBONYL YLIDES [J].
ANDO, W ;
HAGIWARA, K ;
SEKIGUCHI, A .
ORGANOMETALLICS, 1987, 6 (10) :2270-2271
[5]   EVIDENCE OF FORMATION OF OXASILACYCLOPROPANE FROM REACTION OF SILYLENE WITH KETONE [J].
ANDO, W ;
IKENO, M ;
SEKIGUCHI, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (19) :6447-6449
[6]   Reactions of a cyclotrisilane with styrene derivatives and diarylacetylenes - evidence for nucleophilic silylenes [J].
Belzner, J ;
Dehnert, U ;
Ihmels, H .
TETRAHEDRON, 2001, 57 (03) :511-517
[7]   Reactions of a silanediyl with carbon-oxygen and carbon-nitrogen double bonds [J].
Belzner, J ;
Ihmels, H ;
Pauletto, L ;
Noltemeyer, M .
JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (10) :3315-3319
[8]  
BROWNBRIDGE P, 1983, SYNTHESIS-STUTTGART, P1
[9]   New aspects of the Ireland and related Claisen rearrangements [J].
Chai, YH ;
Hong, SP ;
Lindsay, HA ;
McFarland, C ;
McIntosh, MC .
TETRAHEDRON, 2002, 58 (15) :2905-2928
[10]   Metal-catalyzed di-tert-butylsilylene transfer:: Synthesis and reactivity of silacyclopropanes [J].
Cirakovic, J ;
Driver, TG ;
Woerpel, KA .
JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (12) :4007-4012