吉林大学张越涛团队报道了受阻Lewis对使用水氧化剂催化氢硅烷转化为硅醇。相关研究成果于2024年10月16日发表在《美国化学会杂志》。

由于其独特的性质，硅烷醇引起了人们的广泛关注，但使用H₂O作为绿色氧化剂从氢硅烷的有机催化氧化制备仍然具有挑战性。

该文中，研究人员采用受阻路易斯对（FLP）成功抑制了不需要的硅氧烷的形成，并在H₂O的存在下以高到优异的收率生产硅烷醇。

机理研究表明，反应是由H₂O而不是硅烷活化FLP引发的，并通过协同SN₂机制进行。更重要的是，FLP催化的氢硅烷氧化与B(C6F5)3-催化的脱氢的结合，能够实现序列控制低聚硅氧烷的精确合成。

该方法具有广阔的基板范围，易于扩大规模，因此在含硅聚合物材料的精密合成中具有广阔的应用前景。

附：英文原文

Title: Frustrated Lewis Pair-Promoted Organocatalytic Transformation of Hydrosilanes into Silanols with Water Oxidant

Author: Fuyu Xie, Sutao Zhang, Mo Yang, Jianghua He, Shuhua Li, Yuetao Zhang

Issue&Volume: October 16, 2024

Abstract: Owing to their unique properties, the silanols have attracted intense attention but remain challenging to prepare from the organocatalytic oxidation of hydrosilanes using H2O as a green oxidant. Herein, we employ a frustrated Lewis pair (FLP) to successfully suppress the formation of undesired siloxanes and produce silanols in high to excellent yields in the presence of H2O. Mechanistic studies suggest that the reaction is initiated with the activation of FLP by H2O rather than by silanes and goes through a concerted SN2 mechanism. More importantly, the combination of the FLP-catalyzed oxidation of hydrosilanes with B(C6F5)3-catalyzed dehydrogenation enables us to realize the precise synthesis of sequence-controlled oligosiloxanes. This method exhibits a broad substrate scope and can be easily scaled up, thus exhibiting promising application potentials in the precision synthesis of silicon-containing polymer materials.

DOI: 10.1021/jacs.4c07818

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c07818