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一种通过极性反转实现的铜催化区域选择性氢胺化制备α-氨基酸的方法。

An umpolung-enabled copper-catalysed regioselective hydroamination approach to α-amino acids.

作者信息

Nishino Soshi, Miura Masahiro, Hirano Koji

机构信息

Department of Applied Chemistry, Graduate School of Engineering, Osaka University Suita Osaka 565-0871 Japan

Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University Suita Osaka 565-0871 Japan.

出版信息

Chem Sci. 2021 Jul 27;12(34):11525-11537. doi: 10.1039/d1sc03692k. eCollection 2021 Sep 1.

DOI:10.1039/d1sc03692k
PMID:34567503
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8409476/
Abstract

A copper-catalysed regio- and stereoselective hydroamination of acrylates with hydrosilanes and hydroxylamines has been developed to afford the corresponding α-amino acids in good yields. The key to regioselectivity control is the use of hydroxylamine as an umpolung, electrophilic amination reagent. Additionally, a judicious choice of conditions involving the CsOPiv base and DTBM-dppbz ligand of remote steric hindrance enables the otherwise challenging C-N bond formation at the α position to the carbonyl. The point chirality at the β-position is successfully controlled by the Xyl-BINAP or DTBM-SEGPHOS chiral ligand with similarly remote steric bulkiness. The combination with the chiral auxiliary, (-)-8-phenylmenthol, also induces stereoselectivity at the α-position to form the optically active unnatural α-amino acids with two adjacent stereocentres.

摘要

已开发出一种铜催化的丙烯酸酯与硅烷和羟胺的区域和立体选择性氢胺化反应，以高产率得到相应的α-氨基酸。区域选择性控制的关键是使用羟胺作为极性反转的亲电胺化试剂。此外，明智地选择涉及CsOPiv碱和具有远程空间位阻的DTBM-dppbz配体的条件，能够在羰基的α位形成原本具有挑战性的C-N键。通过具有类似远程空间体积的Xyl-BINAP或DTBM-SEGPHOS手性配体成功控制了β位的点手性。与手性助剂(-)-8-苯基薄荷醇的组合也在α位诱导立体选择性，以形成具有两个相邻立体中心的光学活性非天然α-氨基酸。

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