Mn(OAc)3 Promoted α-C—H Phosphonation of α-Oxo Ketene Dithioacetals with Dialkyl Phosphonates

doi:10.6023/cjoc202510001

Abstract

The Mn(OAc)₃ promoted α-C—H phosphonation of α-oxo ketene dithioacetals with dialkyl phosphonates for the synthesis of α-phosphonoketene dithioacetal derivates is developed. The reaction not only features mild reaction conditions, excellent yields and broad substrate scope, but also enables gram-scale reaction, laying the foundation for further chemical transformations of α-phosphonoketene dithioacetal derivates.

Key words: ketene dithioacetals, dialkyl phosphonates, manganese triacetate, vinyl phosphonates

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Haifeng Yu, Yutong Sun, Shaohong Zhang, Ke Li, Xiaobo Zhao. Mn(OAc)₃ Promoted α-C—H Phosphonation of α-Oxo Ketene Dithioacetals with Dialkyl Phosphonates[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 925-933.

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Fig. & Tab. 7

Figure 1. Vinyl phosphonate derivatives with biological activity

Scheme 1. Synthesis of α-phosphonyl ketene dithioacetal derivatives

Entry	n(1a)∶n(2a)	Mn(OAc)₃•2H₂O/ equiv.	T/℃	t/h	Yield^b/%
1	1∶1	2.0	25	24	0 (94)^c
2	1∶1	2.0	80	24	32 (57)^c
3	1∶1	2.0	120	24	58 (33)^c
4	2∶3	2.0	120	24	68 (20)^c
5	2∶3	3.0	120	24	76 (16)^c
6	2∶3	4.0	120	24	77 (13)^c
7	1∶2	2.0	120	24	81 (11) ^c
8	1∶2	3.0	120	1.5	93
9	1∶2	4.0	120	1.4	90

Table 1. Screening of reaction conditions

Table 2. Synthesis of α-phosphonoketene dithioacetals 3

Scheme 2. Gram-scale reactions

Scheme 3. Capturing free radical experiments

Scheme 4. Proposed reaction mechanism

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Mn(OAc)₃促进α-羰基二硫缩烯酮与亚磷酸二烃酯的α-C—H膦酯化反应

Mn(OAc)₃ Promoted α-C—H Phosphonation of α-Oxo Ketene Dithioacetals with Dialkyl Phosphonates

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Fig. & Tab. 7

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Mn(OAc)3促进α-羰基二硫缩烯酮与亚磷酸二烃酯的α-C—H膦酯化反应