β-H Regioselective Trifluoromethyl Sulfonylation of Aryl Ethylene

doi:10.6023/cjoc202202014

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (7): 2134-2139.DOI: 10.6023/cjoc202202014 Previous Articles Next Articles

Special Issue: 有机氟化学虚拟合辑

ARTICLES

芳基乙烯β-H区域选择性三氟甲基磺酰化反应

徐琳琳^a, 兰美君^b, 张慕雨^b, 张永琪^b, 冯宇豪^b, 荣良策^b^,^*(), 张金鹏^a^,^*()

^a徐州医科大学公共卫生学院人类遗传和环境医学重点实验室徐州 221004
^b江苏师范大学化学与材料科学学院徐州 221116

收稿日期:2022-02-11 修回日期:2022-04-06 发布日期:2022-08-09
通讯作者: 荣良策, 张金鹏
基金资助:
江苏省高校自然科学研究项目(18KJA150004); 大学生创新创业训练计划项目和江苏省高校品牌专业资助项目

β-H Regioselective Trifluoromethyl Sulfonylation of Aryl Ethylene

Linlin Xu^a, Meijun Lan^b, Muyu Zhang^b, Yongqi Zhang^b, Yuhao Feng^b, Liangce Rong^b(), Jinpeng Zhang^a()

^aSchool of Public Health, Key Laboratory of Human Genetics and Environmental Medicine, Xuzhou Medical University, Xuzhou 221004
^bSchool of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou 221116

Received:2022-02-11 Revised:2022-04-06 Published:2022-08-09
Contact: Liangce Rong, Jinpeng Zhang
Supported by:
Natural Science Foundation of the Jiangsu Higher Education Institutions of China(18KJA150004); Undergraduate Innovation and Entrepreneurship Training Program and the Brand Major of Universities in Jiangsu Province

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Abstract

In the presence of cerium ammonium nitrate, the β-H radical sulfonation reaction of aryl ethylene with sodium trifluoromethanesulfinate was reported to give highly regioselective trans-alkene. The advantages of this method were cheap and easy to obtain reaction reagents, mild reaction conditions and simple operation. Moreover, the reaction had a high regioselective and configurational selectivity.

Key words: aryl ethylene, trifluoromethyl sulfonylation, regioselective reaction, radical

Cite this article

Linlin Xu, Meijun Lan, Muyu Zhang, Yongqi Zhang, Yuhao Feng, Liangce Rong, Jinpeng Zhang. β-H Regioselective Trifluoromethyl Sulfonylation of Aryl Ethylene[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2134-2139.

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References 9

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Entry	Oxidant	Solvent	Temp./℃	Time/h	Yield^b/%
1	CAN (2.0 equiv.)	DMSO	r.t.	6	12
2	CAN (2.0 equiv.)	MeCN	r.t.	6	45
3	CAN (2.0 equiv.)	CH₂Cl₂	r.t.	6	23
4	CAN (2.0 equiv.)	THF	r.t.	6	36
5	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	6	51
6	DTBP (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
7	PhI(OAc)₂ (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
8	TBHP (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
9	AIBN (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
10	AgNO₃(2.0 equiv.)	1,4-Dioxane	r.t.	6	0
11	K₂S₂O₈ (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
12	CAN (2.0 equiv.)	1,4-Dioxane	40	6	30
13	CAN (2.0 equiv.)	1,4-Dioxane	60	6	0
14	CAN (2.0 equiv.)	1,4-Dioxane	80	6	0
15	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	7	65
16	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	8	75
17	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	9	71
18	CAN (1.0 equiv.)	1,4-Dioxane	r.t.	8	31
19	CAN (1.5 equiv.)	1,4-Dioxane	r.t.	8	60
20	CAN (3.0 equiv.)	1,4-Dioxane	r.t.	8	75

Entry	Oxidant	Solvent	Temp./℃	Time/h	Yield^b/%
1	CAN (2.0 equiv.)	DMSO	r.t.	6	12
2	CAN (2.0 equiv.)	MeCN	r.t.	6	45
3	CAN (2.0 equiv.)	CH₂Cl₂	r.t.	6	23
4	CAN (2.0 equiv.)	THF	r.t.	6	36
5	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	6	51
6	DTBP (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
7	PhI(OAc)₂ (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
8	TBHP (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
9	AIBN (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
10	AgNO₃(2.0 equiv.)	1,4-Dioxane	r.t.	6	0
11	K₂S₂O₈ (2.0 equiv.)	1,4-Dioxane	r.t.	6	0
12	CAN (2.0 equiv.)	1,4-Dioxane	40	6	30
13	CAN (2.0 equiv.)	1,4-Dioxane	60	6	0
14	CAN (2.0 equiv.)	1,4-Dioxane	80	6	0
15	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	7	65
16	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	8	75
17	CAN (2.0 equiv.)	1,4-Dioxane	r.t.	9	71
18	CAN (1.0 equiv.)	1,4-Dioxane	r.t.	8	31
19	CAN (1.5 equiv.)	1,4-Dioxane	r.t.	8	60
20	CAN (3.0 equiv.)	1,4-Dioxane	r.t.	8	75

Entry		Product	Yield/%
1	H	3a	75
2	2-CH₃	3b	59
3	3-CH₃	3c	76
4	4-CH₃	3d	84
5	2,5-(CH₃)₂	3e	68
6	3,4-(CH₃)₂	3f	80
7	2,4,6-(CH₃)₃	3g	60
8	4-CH(CH₃)₂	3h	79
9	4-C(CH₃)₃	3i	81
10	4-CH₃O	3j	85
11	4-AcO	3k	78
12	4-F	3l	80
13	3-Cl	3m	56
14	4-Cl	3n	62
15	3-Br	3o	57
16	4-Br	3p	64
17	4-ClCH₂	3q	79
18	2-Br-4-CH₃	3r	57

Entry		Product	Yield/%
1	H	3a	75
2	2-CH₃	3b	59
3	3-CH₃	3c	76
4	4-CH₃	3d	84
5	2,5-(CH₃)₂	3e	68
6	3,4-(CH₃)₂	3f	80
7	2,4,6-(CH₃)₃	3g	60
8	4-CH(CH₃)₂	3h	79
9	4-C(CH₃)₃	3i	81
10	4-CH₃O	3j	85
11	4-AcO	3k	78
12	4-F	3l	80
13	3-Cl	3m	56
14	4-Cl	3n	62
15	3-Br	3o	57
16	4-Br	3p	64
17	4-ClCH₂	3q	79
18	2-Br-4-CH₃	3r	57

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芳基乙烯β-H区域选择性三氟甲基磺酰化反应

β-H Regioselective Trifluoromethyl Sulfonylation of Aryl Ethylene

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