三线态能量转移促进的自由基链式烯烃氢芳基化反应研究

doi:10.6023/cjoc202407045

摘要/Abstract

以碘代芳烃为芳基供体, 报道了一例三线态能量转移促进的自由基链式烯烃氢芳基化反应. 该反应条件绿色温和, 表现出较高的反应效率, 良好的官能团兼容性、底物适用性, 优异的反马氏加成区域选择性, 且可有效放大至克级规模. 炔烃或复杂烯烃底物可有效参与. 原位生成的硅自由基通过卤原子转移促进芳基自由基生成是反应得以发生的关键. 通过底物设计, 该反应亦可应用于四氢喹啉酮药效骨架的合成. 当反应在分子内发生时, 也可使用相对惰性的溴代芳烃为芳基供体. 同时, 初步探索了黄原酸苯酯作为芳基供体进行反应的可行性.

关键词: 三线态能量转移, 卤原子转移, 烯烃氢芳基化, 自由基链式反应, 反马氏加成

A radical chain hydroarylation of alkenes enabled by triplet energy transfer using aryl iodides as aryl donor reagents was reported. The reaction is mild and green, displays high reaction efficiency, good functional group compatibility and substrate applicability, excellent anti-Markovnikov selectivity and could be easily scaled-up to gram scales. Alkynes and complex alkenes were amendable. The halogen-atom transfer (XAT) promoted by in-situ generated silyl radical is crucial for the transformation. The application of the reaction in the synthesis of pharmceutiacally-relavant tetrahydroquinoline scaffold has been also demonstrated via rational design of the substrate. When the reaction occurs intramolecularly, relatively inert aryl bromide could serve as aryl donor. Meanwhile, the feasibility of phenyl xanthate as alternative aryl donor reagent was also preliminarily probed.

Key words: triplet energy transfer, halogen-atom transfer, hydroarylation of alkenes, radical chain reaction, anti-Markovnikov addition

引用此文

郭仕勋, 王卫, 张永强. 三线态能量转移促进的自由基链式烯烃氢芳基化反应研究[J]. 有机化学, 2025, 45(5): 1716-1728.

Shixun Guo, Wei Wang, Yongqiang Zhang. Research of Triplet Energy Transfer Enabled Radical-Chain Hydroarylation of Alkenes[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1716-1728.

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Entry	X	Photocat.	Solvent	Yield^b/%	Entry	X	Photocat.	Solvent	Yield^b/%
1	I	P1 (1 mol%)	MeCN	90	11	I	P7 (3 mol%)	MTBE	68^d
2	I	P2 (3 mol%)	MeCN	72	12	I	P7 (3 mol%)	MTBE	92^e
3	I	P3 (3 mol%)	MeCN	23	13	I	P7 (3 mol%)	MTBE	73^f
4	I	P4 (1 mol%)	MeCN	Trace	14	I	P7 (3 mol%)	MTBE	81^g
5	I	P5 (1 mol%)	MeCN	Trace	15	Br	P7 (3 mol%)	MTBE	Trace
6	I	P6 (3 mol%)	MeCN	Trace	16	Cl	P7 (3 mol%)	MTBE	n.d.^h
7	I	P7 (3 mol%)	MeCN	91	17	I	P7 (3 mol%)	MTBE	Traceⁱ
8	I	P7 (3 mol%)	Toluene	69	18	I	P7 (3 mol%)	MTBE	Trace^j
9	I	P7 (3 mol%)	DMSO	74	19	I	P7 (3 mol%)	MTBE	Trace^k
10	I	P7 (3 mol%)	MTBE	91 (87)^c	20	I	P7 (3 mol%)	MTBE	Trace^l

Entry	X	Photocat.	Solvent	Yield^b/%	Entry	X	Photocat.	Solvent	Yield^b/%
1	I	P1 (1 mol%)	MeCN	90	11	I	P7 (3 mol%)	MTBE	68^d
2	I	P2 (3 mol%)	MeCN	72	12	I	P7 (3 mol%)	MTBE	92^e
3	I	P3 (3 mol%)	MeCN	23	13	I	P7 (3 mol%)	MTBE	73^f
4	I	P4 (1 mol%)	MeCN	Trace	14	I	P7 (3 mol%)	MTBE	81^g
5	I	P5 (1 mol%)	MeCN	Trace	15	Br	P7 (3 mol%)	MTBE	Trace
6	I	P6 (3 mol%)	MeCN	Trace	16	Cl	P7 (3 mol%)	MTBE	n.d.^h
7	I	P7 (3 mol%)	MeCN	91	17	I	P7 (3 mol%)	MTBE	Traceⁱ
8	I	P7 (3 mol%)	Toluene	69	18	I	P7 (3 mol%)	MTBE	Trace^j
9	I	P7 (3 mol%)	DMSO	74	19	I	P7 (3 mol%)	MTBE	Trace^k
10	I	P7 (3 mol%)	MTBE	91 (87)^c	20	I	P7 (3 mol%)	MTBE	Trace^l