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钴卡宾自由基与α-氨烷基自由基的拦截:构建β-酯-γ-氨基酮的串联反应。

Interception of cobalt-based carbene radicals with α-aminoalkyl radicals: a tandem reaction for the construction of β-ester-γ-amino ketones.

机构信息

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China).

出版信息

Angew Chem Int Ed Engl. 2015 Jan 19;54(4):1231-5. doi: 10.1002/anie.201408874. Epub 2014 Nov 25.

Abstract

The interception of cobalt-based carbene radicals with α-aminoalkyl radicals was combined with the Kornblum-DeLaMare reaction and provides β-ester-γ-amino ketones, which are otherwise difficult to obtain in high chemoselectivity. Mechanistically, this transformation is an interplay of cobalt-based carbene radicals, organoradicals, and ionic intermediates and involves the construction of two C-C bonds and one C=O bond in a one-pot process. The reaction also features a wide substrate scope and is highly efficient and insensitive to moisture and air.

摘要

钴卡宾自由基与α-氨烷基自由基的拦截与 Kornblum-DeLaMare 反应相结合,提供了β-酯-γ-氨基酮,否则很难获得高化学选择性。从机理上讲,这种转化是钴基卡宾自由基、有机自由基和离子中间体的相互作用,涉及在一锅过程中构建两个 C-C 键和一个 C=O 键。该反应还具有广泛的底物范围,具有高效、对水分和空气不敏感的特点。

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