Chiral action at a distance: Remote substituent effects on the optical activity of calyculins A and B

被引：11

作者：

Kondru, RK

Beratan, DN ^{[1
]}

Friestad, GK

Smith, AB

Wipf, P

机构：

[1] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA

[2] Univ Vermont, Dept Chem, Burlington, VT 05405 USA

[3] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA

来源：

ORGANIC LETTERS | 2000年 / 2卷 / 11期

关键词：

D O I：

10.1021/ol005634p

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Calyculins A and b differ only by the (E) vs (Z) configuration at C(2). Yet, they show a large difference in optical rotations. We demonstrate a new strategy that provides a physical analysis of this long-range chiro-optical effect by Boltzmann averaged atomic contribution mapping. The polarizability characteristics of the CN substituent rather than the perturbation of the stereogenic centers or the introduction of dissymmetry into the polyene chain give rise to the remarkable difference in rotation angles.

引用

页码：1509 / 1512

页数：4

共 33 条

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[2] POLARIZABILITY THEORY OF OPTICAL-ROTATION [J].