Cobalt-Catalyzed Remote Hydroboration of Enamines

doi:10.6023/cjoc202302027

Abstract

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

Cite this article

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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Fig. & Tab. 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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