单光催化硅烷氢化反应合成双(硅基)和硅硼基烷烃。

IF 8.7 Q1 CHEMISTRY, MULTIDISCIPLINARY
JACS Au Pub Date : 2025-08-22 eCollection Date: 2025-09-22 DOI:10.1021/jacsau.5c00831
Yuki Nagashima, Mone Suzuki, Asuha Shimose, Ryo Arai, Ken Tanaka, Masanobu Uchiyama
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引用次数: 0

摘要

双(硅基)和硅硼基烷烃作为生物活性化合物和高度功能化的合成基石而受到关注,但传统的硅氢化反应在合成含多元素烷烃方面缺乏普遍性和/或选择性。在这里,我们提出了一个多功能的光激活的硅氢化反应,用硅硼烷作为硅基自由基源,构建双(硅基)或硅硼基烷烃。该方法采用单一的吩噻嗪基光催化剂,不需要传统的过渡金属或氢原子转移(HAT)催化剂或助催化剂。因此,它具有很高的通用性,包括含酸/碱敏感基团的烯烃,并提供高的化学/区域选择性,克服了现有方法的局限性。该方法还可以实现二烯的环化官能化和硼基烯烃的芳基硅基化,并且我们表明所获得的含多元素的烷烃是有用的合成构件。机理研究揭示了一种新的光活化机制,与传统的氧化还原或HAT机制相比,吩噻嗪催化剂直接促进Si-B键在三重态下的裂解,从而实现了广泛的烯烃自由基硅氢化反应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Single Photocatalytic Hydrosilylation of Alkenes for the Synthesis of Bis(silyl) and Silaboryl Alkanes.

Bis-(silyl) and silaboryl alkanes are of interest as bioactive compounds and highly functionalized synthetic building blocks, but conventional hydrosilylation reactions lack generality and/or selectivity for synthesizing multielement-containing alkanes. Here, we present a versatile photoactivated hydrosilylation reaction of silicon- or boron-containing alkenes using silylborane as a silyl radical source to construct bis-(silyl) or silaboryl alkanes. This method employs a single phenothiazine-based photocatalyst and does not require conventional transition-metal or hydrogen-atom-transfer (HAT) catalysts or cocatalysts. Consequently, it has high generality, including alkenes bearing acid/base-sensitive groups, and provides high chemo-/regio-selectivity, overcoming the limitations of existing methods. This methodology also enables cyclizative functionalization of dienes and arylsilylation of boryl alkenes, and we show that the obtained multielement-containing alkanes are useful synthetic building blocks. Mechanistic studies uncovered a novel photoactivation mechanism, in which the phenothiazine catalyst directly facilitates Si-B bond cleavage in the triplet state, in contrast to conventional redox or HAT mechanisms, enabling radical hydrosilylation with a broad scope of alkenes.

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来源期刊
CiteScore
9.10
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