钴催化烯胺远程硼氢化

doi:10.6023/cjoc202302027

摘要/Abstract

报道了一例钴催化烯胺的远程硼氢化反应. 此方法使用含量丰富的金属和商业化配体, 通过链行走和硼氢化过程可以快速地构建硼基胺类化合物. 该方法具有反应条件温和、底物普适性广、官能团相容性好等优点. 此外, 通过克级反应和硼胺产物的多样合成转化, 证明了该反应在合成中的实用性和潜在的应用价值.

关键词: 钴, 烯胺, 远程硼氢化, 硼酸酯

A cobalt-catalyzed remote hydroboration of enamines via a sequence of chain walking and hydroboration in the presence of an earth abundant catalyst and a commercially available ligand is reported, providing a rapid access to borylamines. This protocol exhibites mild reaction conditions, broad substrate scope and good functional group compatibility. In addition, the practicability and the potential synthesis value of this reaction were demonstrated by a gram reaction and a variety of synthetic transformations of the borylamine products.

Key words: cobalt, enamines, remote hydroboration, bornic esters

引用此文

刘育园, 雷雅钦, 杨文, 赵万祥. 钴催化烯胺远程硼氢化[J]. 有机化学, 2023, 43(5): 1761-1771.

Yuyuan Liu, Yaqin Lei, Wen Yang, Wanxiang Zhao. Cobalt-Catalyzed Remote Hydroboration of Enamines[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1761-1771.

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图/表 5

Scheme 1. Remote functionalization of alkenes

Entry	Ligand	Solvent	Yield/%
1	Ph₂PCy	THF	ND
2	PPh₃	THF	ND
3	L1	THF	ND
4	L2	THF	ND
5	L3	THF	ND
6	L4	THF	ND
7	L5	THF	ND
8	L6 (tpy)	THF	31
9	L6	DMF	ND
10	L6	Cyclohexane	57
11	L6	Octane	74
12	L6	Toluene	43
13	L6	CPME	60
14	L6	DME	54
15	L6	EA	89

Table 1. Optimization of the reaction conditionsa,b

Table 2. Substrate scope of enaminesa,b

Scheme 2. Deuterium-labeling experiment

Scheme 3. Gram-scale reaction and synthetic applications Reaction conditions: (a) vinylmagnesium bromide (8.0 equiv.), THF, –78 ℃, 0.5 h, then I2 (8.0 equiv.), –78 ℃, 0.5 h; (b) furan, n-BuLi (1.5 equiv.), THF, –78 ℃, 1 h, then N-bromosuccinimide (NBS) (1.5 equiv.), –78 ℃~r.t., 10 h; (c) MeONH2 (3.0 equiv.), n-BuLi (3.0 equiv.), –78 ℃ to 60 ℃, 15 h; (d) Pd2(dba)3 (5 mol%), PPh3 (40 mol%), Ag2O (1.5 equiv.), (4-MeOC6H4)I (2.0 equiv.), THF, 80 ℃, 24 h.

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