Abstract

The recently reported chemoselective reduction of phosphine oxides with 1,3-diphenyldisiloxane (DPDS) has opened up the possibility of additive-free phosphine oxide reductions in catalytic systems. Herein we disclose the use of this new reducing agent as an enabler of phosphorus redox recycling in Wittig, Staudinger, and alcohol substitution reactions. DPDS was successfully utilized in ambient-temperature additive-free redox recycling variants of the Wittig olefination, Appel halogenation, and Staudinger reduction. Triphenylphosphine-promoted catalytic recycling reactions were also facilitated by DPDS. Additive-free triphenylphosphine-promoted catalytic Staudinger reductions could even be performed at ambient temperature due to the rapid nature of phosphinimine reduction, for which we characterized kinetic and thermodynamic parameters. These results demonstrate the utility of DPDS as an excellent reducing agent for the development of phosphorus redox recycling reactions.

中文翻译：

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1,3-二苯基二硅氧烷可实现无添加剂的氧化还原循环反应和三苯基膦的催化作用

摘要

最近报道的用1，3-二苯基二硅氧烷（DPDS）对氧化膦进行化学选择性还原开辟了在催化体系中无添加剂还原氧化膦的可能性。本文中，我们公开了使用这种新的还原剂作为维蒂希，施陶丁格和酒精取代反应中磷氧化还原循环的促进剂。DPDS已成功用于Wittig烯烃化，Appel卤化和Staudinger还原的室温无添加剂氧化还原循环变体。DPDS还促进了三苯膦促进的催化循环反应。由于膦亚胺还原的快速性质，无添加剂三苯膦促进的Staudinger催化还原甚至可以在环境温度下进行，为此我们表征了动力学和热力学参数。