对炔烃的 α-硝基酯的对映选择性加成。
Enantioselective Addition of α-Nitroesters to Alkynes.
机构信息
Department of Chemistry, University of California, Irvine, Irvine, CA, 92697, USA.
出版信息
Angew Chem Int Ed Engl. 2021 Feb 23;60(9):4599-4603. doi: 10.1002/anie.202014015. Epub 2021 Jan 7.
Abstract
By using Rh-H catalysis, we couple α-nitroesters and alkynes to prepare α-amino-acid precursors. This atom-economical strategy generates two contiguous stereocenters, with high enantio- and diastereocontrol. In this transformation, the alkyne undergoes isomerization to generate a Rh -π-allyl electrophile, which is trapped by an α-nitroester nucleophile. A subsequent reduction with In powder transforms the allylic α-nitroesters to the corresponding α,α-disubstituted α-amino esters.
摘要
利用 Rh-H 催化，我们将α-硝基酯和炔烃偶联，制备α-氨基酸前体。这种原子经济性策略生成两个连续的立体中心，具有高对映选择性和非对映选择性控制。在这个转化中，炔烃经历异构化生成 Rh-π-烯丙基亲电试剂，被α-硝基酯亲核试剂捕获。随后用 In 粉还原，将烯丙基α-硝基酯转化为相应的α，α-二取代α-氨基酸酯。
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