HFIP 介导迈克尔受体和艾申莫瑟盐之间的直接 C-C 偶联。

Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.

Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.

Angew Chem Int Ed Engl. 2022 Mar 7;61(11):e202109933. doi: 10.1002/anie.202109933. Epub 2022 Feb 3.

A direct C-C coupling process that merges Michael acceptors and Eschenmoser's salt is presented. Although reminiscent of the Morita-Baylis-Hillman reaction, this process requires no Lewis base catalyst. The underlying mechanism was unveiled by a combination of kinetic, isotopic labelling experiments as well as computational investigations, which showcased the critical role of HFIP as a superior mediator for proton-transfer events as well as the decisive role of the halide counterion.

本文提出了一种直接的 C-C 偶联过程，该过程结合了迈克尔受体和埃申莫瑟盐。虽然这一过程让人联想到 Morita-Baylis-Hillman 反应，但它不需要路易斯碱催化剂。通过动力学、同位素标记实验以及计算研究的结合，揭示了这一过程的潜在机制，这些研究展示了 HFIP 作为质子转移事件的优越介质以及卤化物抗衡离子的决定性作用。