Computational Studies on the Platinum(II)-Catalyzed Cycloisomerization of 1,6-Dienes into Bicyclopropanes: A Mechanistic Quandary Evaluated by DFT

详细信息    查看全文

• 作者：Franziska Bell^† ; ; Jason Holland^† ; ; Jennifer C. Green*^† ; ; Michel R. Gagn^&#8225 ;
• 刊名：Organometallics
• 出版年：2009
• 出版时间：April 13, 2009
• 年：2009
• 卷：28
• 期：7
• 页码：2038-2045
• 全文大小：352K
• 年卷期：v.28,no.7(April 13, 2009)
• ISSN：1520-6041

文摘

The mechanism of the (bis(phosphanylethyl)phosphane)Pt²⁺-catalyzed cycloisomerization reaction of 7-methylocta-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.