铜催化双炔膦氧化物硅质子化反应合成β-硅基取代的乙烯基膦氧化物

doi:10.6023/cjoc202307030

摘要/Abstract

报道了铜催化双炔基膦氧化物单侧硅质子化合成β-硅基取代乙烯基膦氧化物的反应. 各种(杂)芳基和烷基取代的二炔膦氧化物能够以中等和较高的产率和较高的化学选择性得到相应的目标产物. 产物中未反应的炔基可以被进一步衍生为其它官能团.

A copper-catalyzed mono-lateral protosilylation of dialkynylphosphine oxides for the synthesis of β-silyl substituted vinylphosphine oxides is described. Various (hetero)aryl and alkyl-substituted diynes afforded the corresponding products in moderate and high yields with high chemoselectivity. An alternative alkynyl functional group of products could also be further derived.

Key words: copper catalyst, protosilylation, phosphine oxides, β-silyl substituted compounds

引用此文

陈志远, 杨梦维, 徐建林, 徐允河. 铜催化双炔膦氧化物硅质子化反应合成β-硅基取代的乙烯基膦氧化物[J]. 有机化学, 2023, 43(10): 3598-3607.

Zhiyuan Chen, Mengwei Yang, Jianlin Xu, Yunhe Xu. Regioselective Synthesis of β-Silyl-Substituted Vinylphosphine Oxides via Copper-Catalyzed Protosilylation of Dialkynylphosphine Oxides[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3598-3607.

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Entry	Catalyst	Base (equiv.)	Additive (equiv.)	Solvent	Yield^b/%
Entry	Catalyst	Base (equiv.)	Additive (equiv.)	Solvent	3a	4a
1	CuCN	NaOMe (0.75)	MeOH (1.5)	THF	N.D.	0
2	CuCN	Cs₂CO₃ (0.75)	MeOH (1.5)	THF	Trace	0
3	CuBr	Cs₂CO₃ (0.75)	MeOH (1.5)	DCM	12	0
4	CuBr	Cs₂CO₃ (0.15)	MeOH (1.5)	DCM	21	0
5	CuBr·Me₂S	Cs₂CO₃ (0.15)	MeOH (3.0)	DCM	58	4
6	CuBr·Me₂S	Cs₂CO₃ (0.15)	EtOH (3.0)	DCM	61	9
7	CuBr·Me₂S	Cs₂CO₃ (0.15)	H₂O (3.0)	DCM	17	0
8	CuBr·Me₂S	Cs₂CO₃ (0.15)	Phenol (3.0)	DCM	76	8
9	CuBr·Me₂S	CsF (0.15)	Phenol (3.0)	DCM	64	3
10	CuBr·Me₂S	CsOAc (0.15)	Phenol (3.0)	DCM	51	3
11	CuBr·Me₂S	Na₂CO₃ (0.15)	Phenol (3.0)	DCM	N.R.	0
12	CuBr·Me₂S	NaOEt (0.15)	Phenol (3.0)	DCM	N.R.	0
13	CuBr·Me₂S	Cs₂CO₃ (0.15)	Phenol (5.0)	DCM	83	6
14	CuBr·Me₂S	Cs₂CO₃ (0.15)	4-Nitrophenol (5.0)	DCM	57	0
15	CuBr·Me₂S	Cs₂CO₃ (0.15)	1-Naphtol (5.0)	DCM	46	0
16	CuBr·Me₂S	Cs₂CO₃ (0.15)	4-Methoxyphenol (5.0)	DCM	72	2
17	CuBr·Me₂S	Cs₂CO₃ (0.15)	3-Methoxyphenol (5.0)	DCM	93 (86)	5

Entry	Catalyst	Base (equiv.)	Additive (equiv.)	Solvent	Yield^b/%
Entry	Catalyst	Base (equiv.)	Additive (equiv.)	Solvent	3a	4a
1	CuCN	NaOMe (0.75)	MeOH (1.5)	THF	N.D.	0
2	CuCN	Cs₂CO₃ (0.75)	MeOH (1.5)	THF	Trace	0
3	CuBr	Cs₂CO₃ (0.75)	MeOH (1.5)	DCM	12	0
4	CuBr	Cs₂CO₃ (0.15)	MeOH (1.5)	DCM	21	0
5	CuBr·Me₂S	Cs₂CO₃ (0.15)	MeOH (3.0)	DCM	58	4
6	CuBr·Me₂S	Cs₂CO₃ (0.15)	EtOH (3.0)	DCM	61	9
7	CuBr·Me₂S	Cs₂CO₃ (0.15)	H₂O (3.0)	DCM	17	0
8	CuBr·Me₂S	Cs₂CO₃ (0.15)	Phenol (3.0)	DCM	76	8
9	CuBr·Me₂S	CsF (0.15)	Phenol (3.0)	DCM	64	3
10	CuBr·Me₂S	CsOAc (0.15)	Phenol (3.0)	DCM	51	3
11	CuBr·Me₂S	Na₂CO₃ (0.15)	Phenol (3.0)	DCM	N.R.	0
12	CuBr·Me₂S	NaOEt (0.15)	Phenol (3.0)	DCM	N.R.	0
13	CuBr·Me₂S	Cs₂CO₃ (0.15)	Phenol (5.0)	DCM	83	6
14	CuBr·Me₂S	Cs₂CO₃ (0.15)	4-Nitrophenol (5.0)	DCM	57	0
15	CuBr·Me₂S	Cs₂CO₃ (0.15)	1-Naphtol (5.0)	DCM	46	0
16	CuBr·Me₂S	Cs₂CO₃ (0.15)	4-Methoxyphenol (5.0)	DCM	72	2
17	CuBr·Me₂S	Cs₂CO₃ (0.15)	3-Methoxyphenol (5.0)	DCM	93 (86)	5