Racemic but Tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes:: Highly enantioselective ene-type cyclization of 1,6-enynes

被引：62
|
作者：
Mikami, K [1 ]
Kataoka, S [1 ]
Yusa, Y [1 ]
Aikawa, K [1 ]
机构：
[1] Tokyo Inst Technol, Dept Appl Chem, Tokyo 1528552, Japan
来源：
ORGANIC LETTERS | 2004年 / 6卷 / 21期
关键词：
D O I：
10.1021/ol048604l
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degreesC, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.
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页码：3699 / 3701
页数：3
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