东华大学刘为萍团队钳形锰配合物以甲醇为C1源借氢β-磷酸甲基化醇的研究。相关研究成果发表在2023年11月14日出版的《美国化学会杂志》。

该文中，研究人员报道了一种锰催化的含β-H的醇、甲醇和膦的三组分偶联反应，通过借氢策略合成γ-羟基膦。在这一过程中，甲醇是一种可持续的C1来源。各种芳香族和脂肪族取代的醇和膦可以有效地进行脱氢交叉偶联过程，并以中等至良好的产率递送相应的β-亚磷酸单甲基化醇产物。

机理研究表明，这种转化按顺序的方式进行，包括催化脱氢、羟醛缩合、迈克尔加成和催化氢化。

附：英文原文

Title: Borrowing Hydrogen β-Phosphinomethylation of Alcohols Using Methanol as C1 Source by Pincer Manganese Complex

Author: Feixiang Sun, Xin Chen, Siyi Wang, Fan Sun, Sheng-Yin Zhao, Weiping Liu

Issue&Volume: November 14, 2023

Abstract: Herein, we report a manganese-catalyzed three-component coupling of β-H containing alcohols, methanol, and phosphines for the synthesis of γ-hydroxy phosphines via a borrowing hydrogen strategy. In this development, methanol serves as a sustainable C1 source. A variety of aromatic and aliphatic substituted alcohols and phosphines could undergo the dehydrogenative cross-coupling process efficiently and deliver the corresponding β-phosphinomethylated alcohol products in moderate to good yields. Mechanistic studies suggest that this transformation proceeds in a sequential manner including catalytic dehydrogenation, aldol condensation, Michael addition, and catalytic hydrogenation.

DOI: 10.1021/jacs.3c10484

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c10484