无催化剂、无溶剂条件下炔烃和烯烃与儿茶酚硼烷的硼氢化反应

doi:10.6023/cjoc202209011

摘要/Abstract

报道了无催化剂和无溶剂条件下炔烃和烯烃与儿茶酚硼烷的硼氢化反应, 各种芳香族和脂肪族炔烃和烯烃底物分别以高产率和高区域/立体选择性成功地转化为相应的反马氏烯基和烷基硼酸酯产物. 克级硼氢化和多用途转化反应显示了其在实际应用中的巨大潜力. 在相应密度泛函理论(DFT)计算的基础上, 提出了一种可能的反应机理.

关键词: 绿色化学, 硼氢化, 无催化剂, 炔烃, 烯烃

A catalyst-free and solvent hydroboration of alkynes and alkenes with catecholborane was reported. Various alkynes and alkenes including aromatic and aliphatic groups were smoothly converted into the corresponding anti-Markovnikov alkenyl and alkyl boronate esters in high yields and high regio/stereoselectivity at room temperature and 50 ℃, respectively. The gram-scale hydroboration and further versatile conversions demonstrated great potential in the practical application. A plausible reaction mechanism was proposed based on the corresponding density function theory (DFT) calculations.

Key words: green chemistry, hydroboration, catalyst-free, alkyne, alkene

引用此文

卢凯, 屈浩琦, 陈樨, 秋慧, 郑晶, 马猛涛. 无催化剂、无溶剂条件下炔烃和烯烃与儿茶酚硼烷的硼氢化反应[J]. 有机化学, 2023, 43(6): 2197-2205.

Kai Lu, Haoqi Qu, Xi Chen, Hui Qiu, Jing Zheng, Mengtao Ma. Catalyst-Free and Solvent-Free Hydroboration of Alkynes and Alkenes with Catecholborane[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2197-2205.

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图/表 8

Scheme 1. Hydroboration of alkynes and alkenes with HBcat

Entry	n	Temp./℃	Time/h	Solvent	Conv.^a/%
1	1.1	r.t.	12	CDCl₃	70
2	1.2	r.t.	6		76
3	1.2	r.t.	12		99
4	1.2	r.t.	12	CDCl₃	99
5	1.2	40	6		80
6	1.2	40	12		99
7	3.0	r.t.	12		99
8	3.0	110	12	CDCl₃	99

Table 1. Optimization of reaction conditions for 4-ethynyl- toluene with HBcat

Table 2. Hydroboration of various alkynes with HBcata

Entry	n	Temp./℃	Time/h	Conv.^a/%
1	1.2	rt	12	12
2	1.2	50	12	76
3	1.2	50	20	81
4	1.5	50	20	99

Table 3. Optimization of reaction conditions for styrene with HBcat

Table 4. Hydroboration of various alkenes with HBcata

Scheme 2. (a) Scale-up hydroboration of phenylacetylene, (b) transformation of 1a to more stable 3a and (c) Suzuki-coupling reaction of 1a

Scheme 3. Proposed mechanism for the hydroboration of alkynes and alkenes

Figure 1. DFT calculations for the hydroboration of phenylacetylene (a, 298.15 K) and styrene (b, 323.15 K)

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