tert-Butyl Hydroperoxide-Mediated Synthesis of Phosphoroselenoates

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.Keywords tert-butyl hydroperoxide; diselenide; phosphite; phosphoroselenoate 磷酸硒酯(phosphoroselenoate)骨架结构是一种重要 的有机结构基础单元, 广泛存在于生物活性分子中 [1] (图 1), 在有机合成中也具有较大的应用价值 [2] .因此该 类化合物的合成研究得到化学家们的广泛关注. 早期合 成这类化合物的主要方法包括使用苯基卤化硒与亚磷 酸三烷基酯反应或者苯硒化锂与 O,O-二烷基膦酰氯反 应 [2a,3] .但这些原料的制备需要使用毒性试剂如氯气、 溴 素, 此外, 这些原料对空气敏感, 因此反应条件苛刻, 反应操作繁琐.二硒醚化合物作为非常稳定且容易操作的硒源一 直是合成化学家从事有机硒化学研究的首选目标 [4] .近 年来, 通过活化二硒醚化合物与亚磷酸酯反应来制备硒 代磷酸酯化合物报道较多.