Asymmetric Morita-Baylis-Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back-Reaction Screening

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• 作者：Patrick G. Isenegger ; Dr. Florian Bä ; chle and Prof. Dr. Andreas Pfaltz
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：22
• 期：49
• 页码：17595-17599
• 全文大小：887K
• ISSN：1521-3765

文摘

An efficient protocol for the evaluation of catalysts for the asymmetric Morita–Baylis–Hillman (MBH) reaction was developed. By mass spectrometric back-reaction screening of quasi-enantiomeric MBH products, an efficient bifunctional phosphine catalyst was identified that outperforms literature-known catalysts in the MBH reaction of methyl acrylate with aldehydes. The close match between the selectivities measured for the forward and back reaction and kinetic measurements provided strong evidence that the aldol step and not the subsequent proton transfer is rate- and enantioselectivity-determining.