三价磷/五价磷催化的芳基硼酸和酯的甲胺化反应：以硝基甲烷作为甲胺替代物的还原 C-N 偶联。
P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C-N Coupling with Nitromethane as a Methylamine Surrogate.
机构信息
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
出版信息
J Am Chem Soc. 2020 Sep 23;142(38):16205-16210. doi: 10.1021/jacs.0c08035. Epub 2020 Sep 11.
Abstract
The direct reductive -arylation of nitromethane by organophosphorus-catalyzed reductive C-N coupling with arylboronic acid derivatives is reported. This method operates by the action of a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane -oxide) together with a mild terminal reductant hydrosilane to drive the selective installation of the methylamino group to (hetero)aromatic boronic acids and esters. This method also provides for a unified synthetic approach to isotopically labeled -methylanilines from various stable isotopologues of nitromethane (i.e., CDNO, CHNO, and CHNO), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.
摘要
报道了膦催化的还原 C-N 偶联反应，实现了硝基甲烷与芳基硼酸衍生物的直接还原芳基化。该方法通过使用小环有机磷催化剂（1,2,2,3,4,4-六甲基磷杂环丁烷氧化物）和温和的末端还原剂氢化硅烷的共同作用，选择性地将甲氨基基团安装到（杂）芳基硼酸和酯上。该方法还为从各种稳定的硝基甲烷同位素（即 CDNO、CHNO 和 CHNO）中得到同位素标记的 - 甲基苯胺提供了一种统一的合成方法，表明这种易于处理的化合物是直接安装甲氨基基团的多功能前体。
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