关于铂（II）催化1,6 - 二烯环异构化为双环丙烷的计算研究：通过密度泛函理论评估的机理难题
Computational Studies on the Pt(II)-Catalyzed Cycloisomerization of 1,6-dienes into Bicyclopropanes: A Mechanistic Quandary Evaluated by DFT.
作者信息
Bell Franziska, Holland Jason, Green Jennifer C, Gagné Michel R
机构信息
The Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR, United Kingdom.
出版信息
Organometallics. 2009 Apr 13;28(7):2038-2045. doi: 10.1021/om800760x.
Abstract
The mechanism of the (bis(phosphanylethyl)phosphane)Pt(2+) catalyzed cyclo-isomerization reaction of 7-methyl-octa-1,6-diene to form 1-isopropylbicyclo[3.1.0]hexane was studied using computational methods. The cyclopropanation step was found to be the turnover-limiting step. The overall reaction proceeds via both a 5-exo and a 6-endo route. W conformations were shown to facilitate cyclopropanation, but do not have any influence on the rate of the 1,2-hydride shifts.
摘要
使用计算方法研究了（双（膦基乙基）膦烷）铂（2+）催化7-甲基-1,6-辛二烯环异构化反应生成1-异丙基双环[3.1.0]己烷的机理。发现环丙烷化步骤是周转限制步骤。整个反应通过5-外向和6-内向两条途径进行。W构象被证明有助于环丙烷化，但对1,2-氢化物迁移速率没有任何影响。
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