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光氧化还原/镍双催化炔丙基碳酸酯的区域选择性烷基化反应合成三取代丙二烯。

Photoredox/nickel dual-catalyzed regioselective alkylation of propargylic carbonates for trisubstituted allenes.

机构信息

College of Chemistry and Food Science, Nanchang Normal University, Nanchang, 330000, P. R. China.

State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, P. R. China.

出版信息

Chem Commun (Camb). 2021 Sep 16;57(74):9390-9393. doi: 10.1039/d1cc03303d.

Abstract

Herein, a highly regioselective alkylation of propargylic carbonates for trisubstituted allenes with alkyl 1,4-dihydropyridine derivatives (1,4-DHPs) is developed a photoredox/nickel dual-catalyzed process, which represents the first direct approach to access alkylated allene products without alkyl organometallic reagents. This method features a broad substrate scope and mild conditions. A hypothetical mechanism with an alkyl radical and an allenyl Ni(III) species is proposed. Benzylation products were also obtained to be the complement building blocks for the potential synthesis of pharmaceuticals.

摘要

本文开发了一种通过光还原/镍双催化过程,高区域选择性地将丙炔碳酸酯与烷基 1,4-二氢吡啶衍生物(1,4-DHPs)烷基化,得到三取代的丙二烯。这是首次在没有烷基有机金属试剂的情况下,直接得到烷基化丙二烯产物的方法。该方法具有广泛的底物范围和温和的条件。提出了一个包含烷基自由基和烯丙基 Ni(III)物种的假设机制。还获得了苄基化产物,它们是潜在药物合成的补充构建块。

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