Visible-Light Induced Hydrophosphination of Olefins

doi:10.6023/cjoc202512046

Abstract

The hydrophosphination of olefins represents a fundamental strategy for the construction of P—C bonds in organic synthesis. A distinct protocol for the synthesis of tertiary phosphine compounds via visible light-catalyzed hydrophosphination of alkenes was developed. The reaction features a broad substrate scope and exceptional functional group compatibility, affording a diverse array of tertiary phosphine products with moderate to excellent yields ranging from 48% to 95%. A plausible reaction mechanism has been proposed. Specifically, photoexcited-catalyst-mediated single-electron oxidation of diphenyl- phosphine generates the corresponding phosphine radical cations (PRCs), which subsequently undergo radical addition across the carbon-carbon double bonds of alkenes. Furthermore, the formation of quaternary phosphonium salt and trivalent phosphine species was detected by ³¹P NMR spectroscopy, providing direct evidence for the reaction mechanism.

Key words: alkene hydrophosphination, phosphine radical cation, photocatalysis

Cite this article

Ziliang Yuan, Bingdong Li, Dinghai Wang. Visible-Light Induced Hydrophosphination of Olefins[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1677-1684.

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Entry	Variation from the “standard conditions”	Yield^b/%
1	None	89
2	2,4,6-Trimethylbenzenethiol in place of PhS-SPh	31
3	CF₃SO₃H (1.0 equiv.) was used	60
4	CH₃COOH (1.0 equiv.) in place of CF₃SO₃H	23
5	CF₃COOH (1.0 equiv.) in place of CF₃SO₃H	26
6	2a (1.5 equiv.) was used	39
7	Ir(ppy)₃ in place of [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	22
8	4-CzIPN in place of [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	12
9	Eosin Y in place of [Ir[dF(CF₃)ppy_]2(dtbbpy)]PF₆	3
10	DCE in place of CH₃CN	49
11	DMF in place of CH₃CN	41
12	THF in place of CH₃CN	14
13	Without [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	5
14	Without light	0

Entry	Variation from the “standard conditions”	Yield^b/%
1	None	89
2	2,4,6-Trimethylbenzenethiol in place of PhS-SPh	31
3	CF₃SO₃H (1.0 equiv.) was used	60
4	CH₃COOH (1.0 equiv.) in place of CF₃SO₃H	23
5	CF₃COOH (1.0 equiv.) in place of CF₃SO₃H	26
6	2a (1.5 equiv.) was used	39
7	Ir(ppy)₃ in place of [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	22
8	4-CzIPN in place of [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	12
9	Eosin Y in place of [Ir[dF(CF₃)ppy_]2(dtbbpy)]PF₆	3
10	DCE in place of CH₃CN	49
11	DMF in place of CH₃CN	41
12	THF in place of CH₃CN	14
13	Without [Ir[dF(CF₃)ppy]₂(dtbbpy)]PF₆	5
14	Without light	0

可见光催化的烯烃氢膦化反应