铜催化芳基重氮乙酸酯与双[(频哪醇)硼基]甲烷的偶联反应

doi:10.6023/cjoc202301027

摘要/Abstract

报道铜催化下重氮苯乙酸酯作为卡宾前体与双[(频哪醇)硼基]甲烷的交叉偶联反应, 实现sp³-杂化碳碳键的构筑. 条件筛选表明亚磷酰胺配体monophos对该反应的成功尤为关键. 原位氧化使得硼酯产物以醇的形式被分离, 反应具有高效率以及良好的官能团兼容性. 该两步反应是芳基重氮酯类化合物形式上的羟甲基化.

关键词: 铜催化, sp³-杂化碳碳键构筑, 重氮化合物, 双[(频哪醇)硼基]甲烷

The copper-catalyzed cross-coupling reaction of 1,1-bis[(pinacolato)boryl]methane with α-diazophenylacetate as carbene precursor was reported, leading to the construction of C(sp³)—C(sp³) bond. Reaction optimization experiments showed that Monophos ligand was critical for the success of this reaction. In situ oxidation afforded the corresponding primary alcohols instead of the relatively unstable boronates. The reaction has high efficiency and good functional group compatibility. The two-step transformation represents a formal hydroxymethylation of diazoacetates.

Key words: copper catalysis, C(sp³)—C(sp³) bond formation, diazo compounds, bis[(pinacolato)boryl]methane

引用此文

鲍志成, 李慕尧, 王剑波. 铜催化芳基重氮乙酸酯与双[(频哪醇)硼基]甲烷的偶联反应[J]. 有机化学, 2023, 43(5): 1808-1814.

Zhicheng Bao, Muyao Li, Jianbo Wang. Copper-Catalyzed Cross-Coupling of Aryldiazoacetates with Bis[(pinacolato)boryl]methane[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1808-1814.

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Entry	[Cu]	Ligand	Base	Solvent	Yield^b/ %
1	CuCl	Ligand^c	LiO^tBu	Toluene	0
2	CuCl	L1	LiO^tBu	Toluene	24
3	CuCl	L2~L5	LiO^tBu	Toluene	0
4	CuCl	L1	Base^d	Toluene	0
5	CuCl	L1	LiO^tBu	THF	0
6	CuCl	L1	LiO^tBu	DCE	0
7	CuCl	L1	LiO^tBu	m-Xylene	18
8	CuCl	L1	LiO^tBu	Chlorobenzene	14
9	CuCl	L1	LiO^tBu	Trifluorotoluene	8
10^e	CuCl	L1	LiO^tBu	Toluene	38
11^f	CuCl	L1	LiO^tBu	Toluene	52
12	CuBr	L1	LiO^tBu	Toluene	30
13	CuI	L1	LiO^tBu	Toluene	24
14	CuTC	L1	LiO^tBu	Toluene	38
15	Cu(MeCN)₄PF₆	L1	LiO^tBu	Toluene	48
16	CuCl₂	L1	LiO^tBu	Toluene	48
17^g	CuCl	L1	LiO^tBu	Toluene	54
18^h	CuCl	L1	LiO^tBu	Toluene	74

Entry	[Cu]	Ligand	Base	Solvent	Yield^b/ %
1	CuCl	Ligand^c	LiO^tBu	Toluene	0
2	CuCl	L1	LiO^tBu	Toluene	24
3	CuCl	L2~L5	LiO^tBu	Toluene	0
4	CuCl	L1	Base^d	Toluene	0
5	CuCl	L1	LiO^tBu	THF	0
6	CuCl	L1	LiO^tBu	DCE	0
7	CuCl	L1	LiO^tBu	m-Xylene	18
8	CuCl	L1	LiO^tBu	Chlorobenzene	14
9	CuCl	L1	LiO^tBu	Trifluorotoluene	8
10^e	CuCl	L1	LiO^tBu	Toluene	38
11^f	CuCl	L1	LiO^tBu	Toluene	52
12	CuBr	L1	LiO^tBu	Toluene	30
13	CuI	L1	LiO^tBu	Toluene	24
14	CuTC	L1	LiO^tBu	Toluene	38
15	Cu(MeCN)₄PF₆	L1	LiO^tBu	Toluene	48
16	CuCl₂	L1	LiO^tBu	Toluene	48
17^g	CuCl	L1	LiO^tBu	Toluene	54
18^h	CuCl	L1	LiO^tBu	Toluene	74

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