Novikov Roman A, Borisov Denis D, Tarasova Anna V, Tkachev Yaroslav V, Tomilov Yury V
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation.
Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilov st., 119991, Moscow, Russian Federation.
Angew Chem Int Ed Engl. 2018 Aug 6;57(32):10293-10298. doi: 10.1002/anie.201803541. Epub 2018 Jul 17.
A new strategy for the three-component addition of halide anions and acetylenes to donor-acceptor cyclopropanes (DACs) is presented. This reaction, which occurs with high E selectivity, is promoted by gallium(III) salts and based on the 1,2-zwitterionic reactivity of DACs. It opens up a new group of processes involving DACs. The reaction occurs readily with a broad range of substrates and is tolerant of various functional groups. This methodology makes it possible to assemble highly functionalized vinyl halides, which are very convenient building blocks in organic synthesis. A possible mechanism of this reaction and its stereochemical aspects are discussed in detail.
本文提出了一种将卤化物阴离子和乙炔三组分加成到给体-受体环丙烷（DACs）的新策略。该反应具有高E选择性，由镓（III）盐促进，基于DACs的1,2-两性离子反应性。它开辟了一组涉及DACs的新反应过程。该反应能与多种底物顺利发生，并且对各种官能团具有耐受性。这种方法使得组装高度官能化的卤化乙烯成为可能，卤化乙烯是有机合成中非常方便的结构单元。详细讨论了该反应可能的机理及其立体化学方面。
