A bispericyclic transition structure allows for efficient relief of antiaromaticity enhancing reactivity and endo stereoselectivity in the dimerization of the fleeting cyclopentadienone

被引：54

作者：

Quadrelli, P

Romano, S

Toma, L

Caramella, P

机构：

[1] Univ Pavia, Dipartimento Chim Organ, I-27100 Pavia, Italy

[2] Univ Pavia, Dipartimento Fis A Volta, Ist Nazl Fis Mat, I-27100 Pavia, Italy

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 15期

关键词：

D O I：

10.1021/jo034401j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

B3LYP/6-31G* calculations account for the enhanced reactivity and endo stereoselectivity in the dimerization of the fleeting antiaromatic cyclopentadienone. Secondary orbital interactions promote endo stereoselectivity and a full merging of 4+2 and 2+4 allowed paths in an endo bispericyclic transition structure. Electrostatic effects increase reactivity and selectivity but the driving force to enhanced reactivity is the loss of antiaromaticity in the dimerization TSs while enhanced selectivity derives from the more efficient relief of antiaromaticity in the bispericyclic array.

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页码：6035 / 6038

页数：4

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