Cu(OTf)2 Catalyzed Conjugate Addition of Mercaptans to Enones

doi:10.6023/cjoc202012022

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (6): 2424-2434.DOI: 10.6023/cjoc202012022 Previous Articles Next Articles

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三氟甲磺酸铜(II)催化的硫醇对烯酮的共轭加成反应

张同飞, 陈逸波, 高振博^*()

南京农业大学理学院南京 210095

收稿日期:2020-12-14 修回日期:2020-12-06 发布日期:2021-02-26
通讯作者: 高振博
基金资助:
2020年国家级大学生创新训练计划(202010307090)

Cu(OTf)₂ Catalyzed Conjugate Addition of Mercaptans to Enones

Tongfei Zhang, Yibo Chen, Zhenbo Gao()

College of Sciences, Nanjing Agricultural University, Nanjing 210095

Received:2020-12-14 Revised:2020-12-06 Published:2021-02-26
Contact: Zhenbo Gao
Supported by:
Nanjing Agricultural University Research Start-Up Funding, the Jiangsu Shuang Chuang Doctoral Grants in 2019, and the National Program for Student Innovation through Research and Training in 2020(202010307090)

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Abstract

Thioether is a class of compounds with important biological and physiological activities, especially for drugs and natural products, and its efficient synthesis method is one of the research hotspots in organic chemistry. Thia-Michael addition, especially the addition catalyzed by small organic molecules has been widely proved to be an effective method for synthesizing thioether molecules. However, very few studies on transition metal-catalyzed thia-Michael addition have been published and further exploration in this area is needed. In this work, different types of thiol molecules have been effectively added to various cyclic and linear Michael acceptors through the catalysis of copper(II) triflate. To our delight, 42 kinds of sulfide molecules (up to 99% yield) have been efficiently synthesized. This method has many advantages such as mild reaction conditions, wide substrates, simple operation and excellent yield, providing a new method for the preparation of various thioether molecules.

Key words: copper catalysis, conjugate addition, mercaptan

Cite this article

Tongfei Zhang, Yibo Chen, Zhenbo Gao. Cu(OTf)₂ Catalyzed Conjugate Addition of Mercaptans to Enones[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2424-2434.

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Fig. & Tab. 7

References 36

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Entry^a	Catalyst	Solvent	Yield/%^b
1	None	DCM	0
2^c	[Ru(p-cymene)Cl₂]₂	DCM	Tiny
3^c	PdCl₂(PPh₃)₂	DCM	0
4^c	Cp₂ZrCl₂	DCM	0
5^c	Rh₂(OAc)₄	DCM	0
6	Cu₂(OH)₂CO₃	DCM	0
7	CuI	DCM	0
8	CuCl	DCM	Tiny
9	CuSCN	DCM	0
10	Cu(OAc)₂•H₂O	DCM	0
11	Cu(OTf)₂	DCM	81
12	Cu(OTf)₂	DMF	0
13	Cu(OTf)₂	THF	72
14	Cu(OTf)₂	Et₂O	74
15	Cu(OTf)₂	MeCN	72
16	Cu(OTf)₂	EtOH	36
17	Cu(OTf)₂	MeOH	63

Entry^a	Catalyst	Solvent	Yield/%^b
1	None	DCM	0
2^c	[Ru(p-cymene)Cl₂]₂	DCM	Tiny
3^c	PdCl₂(PPh₃)₂	DCM	0
4^c	Cp₂ZrCl₂	DCM	0
5^c	Rh₂(OAc)₄	DCM	0
6	Cu₂(OH)₂CO₃	DCM	0
7	CuI	DCM	0
8	CuCl	DCM	Tiny
9	CuSCN	DCM	0
10	Cu(OAc)₂•H₂O	DCM	0
11	Cu(OTf)₂	DCM	81
12	Cu(OTf)₂	DMF	0
13	Cu(OTf)₂	THF	72
14	Cu(OTf)₂	Et₂O	74
15	Cu(OTf)₂	MeCN	72
16	Cu(OTf)₂	EtOH	36
17	Cu(OTf)₂	MeOH	63

三氟甲磺酸铜(II)催化的硫醇对烯酮的共轭加成反应

Cu(OTf)₂ Catalyzed Conjugate Addition of Mercaptans to Enones

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References 36

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