Copper-Catalyzed Enantioselective Hydroboration of 1-Benzoyl-2,3-dihydropyridin-4(1H)-ones

doi:10.6023/cjoc202602002

Abstract

An efficient copper-catalyzed asymmetric hydroboration of 1-benzoyl-2,3-dihydropyridin-4(1H)-ones is reported. This protocol features a broad substrate scope, tolerating various N-acyl substituents (aryl, naphthoyl, heteroaryl, pivaloyl) and substituted benzoyl moieties, affording cyclic α-aminoboronate esters with up to 99% yield and ee values of 84%~96%. Gram-scale synthesis and downstream transformations demonstrated synthetic utility. A plausible mechanism involving a borylcopper intermediate and σ-bond metathesis is proposed, distinguishing this process from typical Cu-catalyzed alkene hydroborations.

Key words: hydroboration, copper, α-aminoboronate esters

Cite this article

Xiaofei Wu, Wei Sun, Senmiao Xu. Copper-Catalyzed Enantioselective Hydroboration of 1-Benzoyl-2,3-dihydropyridin-4(1H)-ones[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2816-2824.

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Entry	Ligand	[Cu]	Solvent	Yield^b/%	ee^c/%
1	L1	CuCl	Toluene	56	44
2	L2	CuCl	Toluene	22	75
3	L3	CuCl	Toluene	71	93
4	L4	CuCl	Toluene	9	45
5	L5	CuCl	Toluene	Trace	—
6	L6	CuCl	Toluene	Trace	—
7	L3	CuCl	Benzene	20	89
8	L3	CuCl	THF	45	91
9	L3	CuCl	Et₂O	19	93
10	L3	CuCl	MCPE	42	92
11	L3	CuCl	1,4-Dioxane	34	91
12	L3	CuCl	CH₂Cl₂	Trace	—
13	L3	CuCl	CH₃CN	20	91
14	L3	CuCl	n-Hexane	Trace	—
15	L3	CuBr	Toluene	63	93
16	L3	CuTc	Toluene	30	93
17	L3	CuOAc	Toluene	Trace	—
18	L3	Cu(CH₃CN)₄PF₆	Toluene	Trace	—
19	L3	CuCl₂	Toluene	Trace	—
20^d	L3	CuCl	Toluene	72	92

Entry	Ligand	[Cu]	Solvent	Yield^b/%	ee^c/%
1	L1	CuCl	Toluene	56	44
2	L2	CuCl	Toluene	22	75
3	L3	CuCl	Toluene	71	93
4	L4	CuCl	Toluene	9	45
5	L5	CuCl	Toluene	Trace	—
6	L6	CuCl	Toluene	Trace	—
7	L3	CuCl	Benzene	20	89
8	L3	CuCl	THF	45	91
9	L3	CuCl	Et₂O	19	93
10	L3	CuCl	MCPE	42	92
11	L3	CuCl	1,4-Dioxane	34	91
12	L3	CuCl	CH₂Cl₂	Trace	—
13	L3	CuCl	CH₃CN	20	91
14	L3	CuCl	n-Hexane	Trace	—
15	L3	CuBr	Toluene	63	93
16	L3	CuTc	Toluene	30	93
17	L3	CuOAc	Toluene	Trace	—
18	L3	Cu(CH₃CN)₄PF₆	Toluene	Trace	—
19	L3	CuCl₂	Toluene	Trace	—
20^d	L3	CuCl	Toluene	72	92

铜催化1-苯甲酰基-2,3-二氢吡啶-4(1H)-酮的对映选择性硼氢化反应