Enantioselective Homocrotylboration of Aliphatic Aldehydes

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• 作者：Hongkun Lin ; Wenbo Pei ; Hao Wang ; Kendall N. Houk ; Isaac J. Krauss
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：January 9, 2013
• 年：2013
• 卷：135
• 期：1
• 页码：82-85
• 全文大小：332K
• 年卷期：v.135,no.1(January 9, 2013)
• ISSN：1520-5126

文摘

A practical route to optically pure syn-homocrotylation reagents is described, including highly diastereo- and enantioselective preparation of numerous syn-homocrotyl products, as well as several matched mismatched pairs. NMR experiments suggest that the active homocrotylating species is a cyclopropylcarbinyldichloroborane generated by chloride exchange from the PhBCl₂ activator. Computational studies support the intermediacy of chloroboranes and suggest that homoallyl/homocrotyl transfers occur through Zimmerman鈥揟raxler transition states.