Allylmagnesium Halides Do Not React Chemoselectively Because Reaction Rates Approach the Diffusion Limit

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• 作者：Jacquelyne A. Read ; K. A. Woerpel
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：February 17, 2017
• 年：2017
• 卷：82
• 期：4
• 页码：2300-2305
• 全文大小：408K
• ISSN：1520-6904

文摘

Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.