可见光诱导杂芳烃与脂肪醇的羟烷基化反应

doi:10.6023/cjoc202112032

摘要/Abstract

发展了一种有效的可见光诱导的杂芳烃与脂肪醇的直接交叉脱氢偶联. 该反应在水溶液中由过硫酸盐引发, 不需要使用化学计量酸来活化杂环. 通过氢原子转移(HAT)从醇瞬时生成的α-羟烷基自由基与一系列杂芳烃发生Minisci反应. 该方法具有无需光催化剂、溶剂绿色环保、反应条件温和、起始材料容易获得和官能团耐受性广泛等优点.

关键词: 醇, 交叉脱氢偶联, 杂芳烃, 羟烷基化, 可见光诱导

An efficient visible light-induced direct cross-dehydrogenative coupling of heteroarenes with aliphatic alcohols in aqueous solution at ambient temperature was developed. The reaction is initiated by persulfate salts and does not require the use of stoichiometric acid for activation of the heterocycle. α-Hydroxyalkyl radicals transiently generated from alcohols via hydrogen atom transfer (HAT) undergo Minisci-type reactions with a range of heteroarenes. This protocol was highlighted by photocatalyst-free, green solvent, mild conditions, readily available starting materials, and wide functional group tolerance.

Key words: alcohol, cross-dehydrogenative coupling, heteroarene, hydroxyalkylation, visible light-induction

引用此文

徐东平, 黄飞, 汤琳, 张新明, 张武. 可见光诱导杂芳烃与脂肪醇的羟烷基化反应[J]. 有机化学, 2022, 42(5): 1493-1500.

Dongping Xu, Fei Huang, Lin Tang, Xinming Zhang, Wu Zhang. Visible Light-Induced Hydroxyalkylation of Heteroarenes with Aliphatic Alcohols[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1493-1500.

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参考文献 17

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Entry	Oxidant	Light source	Solvent	Yield^b/%
1	DTBP	Purple LEDs	H₂O	32
2	TBHP	Purple LEDs	H₂O	Trace
3	H₂O₂	Purple LEDs	H₂O	12
4	DDQ	Purple LEDs	H₂O	Trace
5	TBPB	Purple LEDs	H₂O	53
6	K₂S₂O₈	Purple LEDs	H₂O	43
7	(NH₄)₂S₂O₈	Purple LEDs	H₂O	85
8^c	(NH₄)₂S₂O₈	Purple LEDs	H₂O	61
9^d	(NH₄)₂S₂O₈	Purple LEDs	H₂O	38
10	—	Purple LEDs	H₂O	nr
11	(NH₄)₂S₂O₈	Purple LEDs	DMSO	62
12	(NH₄)₂S₂O₈	Purple LEDs	CH₃CN	46
13	(NH₄)₂S₂O₈	Purple LEDs	—	36
14	(NH₄)₂S₂O₈	White LEDs	H₂O	48
15	(NH₄)₂S₂O₈	Blue LEDs	H₂O	72
16	(NH₄)₂S₂O₈	Green LEDs	H₂O	28
17^e	(NH₄)₂S₂O₈	Sunlight	H₂O	34
18	(NH₄)₂S₂O₈	Darkness	H₂O	nr
19^f	(NH₄)₂S₂O₈	Purple LEDs	H₂O	54
20^g	(NH₄)₂S₂O₈	Purple LEDs	H₂O	51
21^h	(NH₄)₂S₂O₈	Purple LEDs	H₂O	93

Entry	Oxidant	Light source	Solvent	Yield^b/%
1	DTBP	Purple LEDs	H₂O	32
2	TBHP	Purple LEDs	H₂O	Trace
3	H₂O₂	Purple LEDs	H₂O	12
4	DDQ	Purple LEDs	H₂O	Trace
5	TBPB	Purple LEDs	H₂O	53
6	K₂S₂O₈	Purple LEDs	H₂O	43
7	(NH₄)₂S₂O₈	Purple LEDs	H₂O	85
8^c	(NH₄)₂S₂O₈	Purple LEDs	H₂O	61
9^d	(NH₄)₂S₂O₈	Purple LEDs	H₂O	38
10	—	Purple LEDs	H₂O	nr
11	(NH₄)₂S₂O₈	Purple LEDs	DMSO	62
12	(NH₄)₂S₂O₈	Purple LEDs	CH₃CN	46
13	(NH₄)₂S₂O₈	Purple LEDs	—	36
14	(NH₄)₂S₂O₈	White LEDs	H₂O	48
15	(NH₄)₂S₂O₈	Blue LEDs	H₂O	72
16	(NH₄)₂S₂O₈	Green LEDs	H₂O	28
17^e	(NH₄)₂S₂O₈	Sunlight	H₂O	34
18	(NH₄)₂S₂O₈	Darkness	H₂O	nr
19^f	(NH₄)₂S₂O₈	Purple LEDs	H₂O	54
20^g	(NH₄)₂S₂O₈	Purple LEDs	H₂O	51
21^h	(NH₄)₂S₂O₈	Purple LEDs	H₂O	93