1,2-Keto-phosphoro(di)thiolation of Alkenes Enabled by Direct Photolysis of S-Hydrogen Phosphoro(di)thioates

doi:10.6023/cjoc202604015

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (10): 4108-4118.DOI: 10.6023/cjoc202604015 Previous Articles Next Articles

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基于S-氢(二)硫代磷酸酯直接光解实现烯烃1,2-酮-(二)硫代磷酸酯化

王司渝, 黎炜^*(), 蔡志华, 何林^*()

石河子大学化学化工学院新疆石河子 832000

收稿日期:2026-04-08 修回日期:2026-05-10 发布日期:2026-06-08
通讯作者: 黎炜, 何林
基金资助:
新疆天山人才研究项目(2023TSYCCX0122); 石河子大学高层次人才启动基金(RCZK201909)

1,2-Keto-phosphoro(di)thiolation of Alkenes Enabled by Direct Photolysis of S-Hydrogen Phosphoro(di)thioates

Siyu Wang, Wei Li^*(), Zhihua Cai, Lin He^*()

School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832000

Received:2026-04-08 Revised:2026-05-10 Published:2026-06-08
Contact: Wei Li, Lin He
Supported by:
Tianshan Talent Research Project of Xinjiang(2023TSYCCX0122); Start-Up Fund for High-Level Talents of Shihezi University(RCZK201909)

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Abstract

A catalyst-free, visible-light-driven 1,2-keto-phosphoro(di)thiolation of alkenes is reported. This method utilizes tert-butyl hydroperoxide (TBHP) and S-hydrogen phosphoro(di)thioates as difunctionalization reagents to produce β-keto phosphorothioates and β-keto phosphorodithioates in a single step. Preliminary mechanistic studies suggest that the key thiophosphoryl radicals are likely generated not via oxidation by TBHP, but through direct photolysis of S-hydrogen phosphoro(di)thioates. Furthermore, this photochemical protocol features mild conditions and broad substrate scope while obviating the need for external metals, photocatalysts, or bases, providing a sustainable and efficient method for the synthesis of β-keto phosphor(di)thioates.

Key words: visible-light-driven, bifunctional reaction, β-keto phosphor(di)thioate

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Siyu Wang, Wei Li, Zhihua Cai, Lin He. 1,2-Keto-phosphoro(di)thiolation of Alkenes Enabled by Direct Photolysis of S-Hydrogen Phosphoro(di)thioates[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4108-4118.

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Fig. & Tab. 9

References 17

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Entry	Deviation from standard conditions	Yield^b^/%
1	None	82 (76)^c
2	370 nm instead of 395 nm	35
3	427, 440 or 456 nm instead of 395 nm	17, n.d. or n.d.^d
4	Acetone instead of EtOAc	50
5	CH₃OH instead of EtOAc	<10
6	DCM instead of EtOAc	37
7	DMSO instead of EtOAc	13
8	MeCN instead of EtOAc	37
9	^tBuOOH (5.0~6.0 mol/L in decane)	92 (88)
10	Open to air	75
11	Without ^tBuOOH, O₂ instead of Ar	n.d.^d
12	No light, r.t.	Trace
13	No light, 80 ℃	<10

Entry	Deviation from standard conditions	Yield^b^/%
1	None	82 (76)^c
2	370 nm instead of 395 nm	35
3	427, 440 or 456 nm instead of 395 nm	17, n.d. or n.d.^d
4	Acetone instead of EtOAc	50
5	CH₃OH instead of EtOAc	<10
6	DCM instead of EtOAc	37
7	DMSO instead of EtOAc	13
8	MeCN instead of EtOAc	37
9	^tBuOOH (5.0~6.0 mol/L in decane)	92 (88)
10	Open to air	75
11	Without ^tBuOOH, O₂ instead of Ar	n.d.^d
12	No light, r.t.	Trace
13	No light, 80 ℃	<10

基于S-氢(二)硫代磷酸酯直接光解实现烯烃1,2-酮-(二)硫代磷酸酯化

1,2-Keto-phosphoro(di)thiolation of Alkenes Enabled by Direct Photolysis of S-Hydrogen Phosphoro(di)thioates

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Fig. & Tab. 9

References 17

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