叔丁基过氧化氢介导的磷酸硒酯合成

doi:10.6023/cjoc202107053

摘要/Abstract

磷酸硒酯化合物广泛应用于有机合成和药物发现等相关领域. 因此, 开发高效简便合成该类化合物的新方法受到化学家的广泛关注. 报道了一种以叔丁基过氧化氢(TBHP)为氧化剂, 在温和的反应条件下实现了亚磷酸酯和二硒醚偶联反应制备硒代磷酸酯方法. 与现有方法相比, 该方法具有条件温和、底物适用范围广泛、产率高、且不需过渡金属和强碱等优点.

关键词: 叔丁基过氧化氢, 二硒醚, 亚磷酸酯, 磷酸硒酯

Phosphoroselenoates have found widespread applications in the fields of organic synthesis and drug discovery. To this end, continuous efforts have been devoted to the development of novel and efficient methods for the synthesis of these compounds. A new method for the synthesis of phosphoroselenoates through oxidative coupling reaction of diselenides with phosphites by the utilization of t-butyl hydroperoxide (TBHP) as oxidant was herein developed. The distinct advantages of this protocol over all previous methods include mild reaction conditions, broad substrate scope, excellent yields, as well as transition metal- and base-free.

Key words: tert-butyl hydroperoxide, diselenide, phosphite, phosphoroselenoate

引用此文

张云倩, 周晨凡, 刘功清. 叔丁基过氧化氢介导的磷酸硒酯合成[J]. 有机化学, 2022, 42(1): 218-225.

Yunqian Zhang, Chenfan Zhou, Gongqing Liu. tert-Butyl Hydroperoxide-Mediated Synthesis of Phosphoroselenoates[J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 218-225.

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图/表 7

图1. 含磷酸硒酯的生物活性分子

Figure 1. Bioactive molecules containing phosphoroselenoates

图式1. 硒代磷酸酯的合成

Scheme 1. Synthesis of phosphoroselenoates

Entry	Oxidant	Solvent	Time/h	Isolated yield/%
1	PhIO	EtOAc	5	43
2	PhI(OAc)₂	EtOAc	5	35
3	K₂S₂O₈	EtOAc	5	45
4	(NH₄)₂S₂O₈	EtOAc	5	40
5	I₂O₅	EtOAc	5	26
6	Oxone	EtOAc	5	51
7	mCPBA	EtOAc	5	45
8	TBHP	EtOAc	5	65
9	O₂	EtOAc	5	30
10	TBHP	DMSO	5	88
11	TBHP	DMF	5	65
12	TBHP	EtOH	5	55
13	TBHP	THF	5	50
14	TBHP	Hexane	5	56
15	TBHP	Acetone	5	70
16^b	TBHP	DMSO	5	76
17^c	TBHP	DMSO	5	65
18	TBHP	DMSO	2	89
19	TBHP	DMSO	1	73
20	—	DMSO	2	trace

表1. 反应条件的优化a

Table 1. Optimization of reaction conditions

表2. 亚磷酸酯底物的拓展a

Table 2. Expansion of phosphites

表3. 二硫族属化合物的拓展a

Table 3. Expansion of dichalcogenides

图式2. 对照实验

Scheme 2. Control experiments

图式3. 可能的反应机理

Scheme 3. Proposed mechanism

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