Yuan Yang, Zhao Fengqian, Wu Xiao-Feng
Leibniz-Institut für Katalyse e.V. Albert-Einstein-Straße 29a 18059 Rostock Germany
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences 116023 Dalian Liaoning China
Chem Sci. 2021 Aug 25;12(38):12676-12681. doi: 10.1039/d1sc04210f. eCollection 2021 Oct 6.
Secondary amides are omnipresent structural motifs in peptides, natural products, pharmaceuticals, and agrochemicals. The copper-catalyzed enantioselective hydroaminocarbonylation of alkenes described in this study provides a direct and practical approach for the construction of α-chiral secondary amides. An electrophilic amine transfer reagent possessing a 4-(dimethylamino)benzoate group was the key to the success. This method also features broad functional group tolerance and proceeds under very mild conditions, affording a set of α-chiral secondary amides in high yields (up to 96% yield) with unprecedented levels of enantioselectivity (up to >99% ee). α,β-Unsaturated secondary amides can also be produced though the method by using alkynes as the substrate.
仲酰胺是肽、天然产物、药物和农用化学品中普遍存在的结构基序。本研究中描述的铜催化烯烃对映选择性氢氨羰基化反应为构建α-手性仲酰胺提供了一种直接且实用的方法。具有4-（二甲基氨基）苯甲酸酯基团的亲电胺转移试剂是成功的关键。该方法还具有广泛的官能团耐受性，并且在非常温和的条件下进行，以高产率（高达96%）和前所未有的对映选择性水平（高达>99% ee）提供了一系列α-手性仲酰胺。通过使用炔烃作为底物，该方法还可以制备α,β-不饱和仲酰胺。
