STEREOSELECTIVE HYDROGEN-TRANSFER REACTIONS INVOLVING ACYCLIC RADICALS - TANDEM SUBSTITUTED TETRAHYDROFURAN FORMATION AND STEREOSELECTIVE REDUCTION - SYNTHESIS OF THE C-17-C-22 SUBUNIT OF IONOMYCIN

被引:57
作者
GUINDON, Y
YOAKIM, C
GORYS, V
OGILVIE, WW
DELORME, D
RENAUD, J
ROBINSON, G
LAVALLEE, JF
SLASSI, A
JUNG, G
RANCOURT, J
DURKIN, K
LIOTTA, D
机构
[1] UNIV MONTREAL,DEPT CHEM,MONTREAL H3C 3J7,PQ,CANADA
[2] EMORY UNIV,DEPT CHEM,ATLANTA,GA 30322
关键词
D O I
10.1021/jo00084a040
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.
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页码:1166 / 1178
页数:13
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