可见光诱导双硼化合成烷基偕二硼酸酯★

doi:10.6023/cjoc202504018

有机化学 ›› 2025, Vol. 45 ›› Issue (9): 3343-3350.DOI: 10.6023/cjoc202504018 上一篇下一篇

研究论文

可见光诱导双硼化合成烷基偕二硼酸酯^★

任博文^a, 方通昌^b, 刘超^a^,^b^,^*()

^a 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州 730000
^b 南京大学化学化工学院绿色化学与工程研究院配位化学国家重点实验室江苏苏州 215163

收稿日期:2025-04-17 修回日期:2025-06-09 发布日期:2025-07-17

Visible-Light-Induced Diborylation to Access gem-Diborylalkanes^★

Bowen Ren^a, Tongchang Fang^b, Chao Liu^a^,^b^,^*()

^a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
^b State Key Laboratory of Coordination Chemistry, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Suzhou, Jiangsu 215163

Received:2025-04-17 Revised:2025-06-09 Published:2025-07-17
Contact: *E-mail: chao.liu@nju.edu.cn
About author:
^★ Academic Papers of the 27^th Annual Meeting of the China Association for Science and Technology.

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摘要/Abstract

成功开发了一种无金属参与的可见光介导策略, 实现了烷基偕二溴化物的高效双硼化转化. 该反应在室温条件下通过可见光诱导激发C—Br键活化. 以B₂cat₂为双硼源, 高效构建了结构多样的烷基偕二硼酸酯类化合物. 通过原位双溴代/双硼化的串联反应实现了醛类化合物到烷基偕二硼酸酯的一锅法转化. 此外, 太阳光也可以用于诱导该反应的转化, 并实现克级规模合成.

关键词: 硼化学, 自由基硼化, 偕二硼化合物, 光诱导反应

A metal-free, visible-light-induced strategy has been developed for the diborylation of gem-dibromoalkanes. This reaction enables the construction of structurally diverse alkyl gem-diboronates at room temperature via visible-light-induced C—Br bond activation using B₂cat₂ as the boron source. Through a tandem in-situ dibromination/diborylation process, a one- pot transformation from aldehydes to alkyl gem-diboronates has been achieved. Additionally, sunlight irradiation has been demonstrated as a viable alternative for inducing this reaction, enabling gram-scale synthesis with practical applicability.

Key words: boron chemistry, radical borylation, gem-diborylalkanes, photoinduced reaction

引用此文

任博文, 方通昌, 刘超. 可见光诱导双硼化合成烷基偕二硼酸酯^★[J]. 有机化学, 2025, 45(9): 3343-3350.

Bowen Ren, Tongchang Fang, Chao Liu. Visible-Light-Induced Diborylation to Access gem-Diborylalkanes^★[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3343-3350.

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图/表 8

Scheme 1. Borylation of gem-dihaloalkanes to synthesize gem-diborylalkanes

Entry	Variation from the standard condition
1	None	82 (81)^b
2	2.0 equiv. B₂cat₂	67
3	B₂(OH)₂ instead of B₂cat₂	n.d.
4	B₂pin₂ instead of B₂cat₂	n.d.
5	Without H₂O	76
6	5.0 equiv. H₂O	66
7	DMAc instead of DMF	59
8	460 nm LEDs instead of 390 nm LEDs	30
9	Dark	4

Table 1. Preliminary investigationa

Table 2. Substrate scopea

Table 3. Tandem reactions from aldehydes to gem-diboryla- lkanesa

Scheme 2. Unsymmetrical formation of gem-diborylalkanes

Table 4. Sunlight induced borylation reactionsa

Scheme 3. Mechanistic experiments

Scheme 4. Proposed mechanism

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可见光诱导双硼化合成烷基偕二硼酸酯^★

Visible-Light-Induced Diborylation to Access gem-Diborylalkanes^★

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可见光诱导双硼化合成烷基偕二硼酸酯★

Visible-Light-Induced Diborylation to Access gem-Diborylalkanes★

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可视化

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可见光诱导双硼化合成烷基偕二硼酸酯^★

Visible-Light-Induced Diborylation to Access gem-Diborylalkanes^★