Unusual intramolecular [2+2] cycloaddition of allyl and vinylidene C=C bonds under mild conditions:: A theoretical analysis

被引：15

作者：

Braña, P

Gimeno, J

Sordo, JA

机构：

[1] Univ Oviedo, Fac Quim, Lab Quim Computac, Dept Quim Fis & Analit, E-33006 Oviedo, Principado Astu, Spain

[2] Univ Oviedo, Dept Quim Organ & Inorgan, Inst Quim Organomet Enrique Moles, Unidad Asociada,CSIC, E-33006 Oviedo, Principado Astu, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 07期

关键词：

D O I：

10.1021/jo035346h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A theoretical analysis allows for the rationalization of the recently reported unusual formation under mild conditions of a cyclobutylidene ring from a diastereoselective [2 + 2] intramolecular cycloaddition of two C=C systems. The reaction takes place by heating in dichloromethane the vinylidene complexes [Ru((eta(5),eta(3)-C9H7){=C=C(R)H}{kappa(1)-(P)-PPh2(C3H5)}(PPh3)] [BF4] (R = Ph, p-Me-C6H4) (1) yielding the bicyclic alkylidene complexes [Ru(eta(5),eta(3)-C9H7){kappa(2)-(P,C)-(=CC(R)HCH2CHCH2-PPh2}(PPh3)][BF4] (2). The proposed mechanism represents an alternative to the classical Woodward-Hoffmann's supra-antara approach.

引用

页码：2544 / 2550

页数：7

共 55 条

[1] Formation of a cyclobutylidene ring: Intramolecular [2+2] cycloaddition of allyl and vinylidene C=C bonds under mild conditions [J].