A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines,Organometallics

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A Universally Applicable Methodology for the Gram-Scale Synthesis of Primary, Secondary, and Tertiary Phosphines
Organometallics ( IF 2.5 ) Pub Date : 2018-01-09 00:00:00 , DOI: 10.1021/acs.organomet.7b00684
N. Ian Rinehart ₁ , Alexander J. Kendall ₁ , David R. Tyler ₁

Affiliation

Although organophosphine syntheses have been known for the better part of a century, the synthesis of phosphines still represents an arduous task for even veteran synthetic chemists. Phosphines as a class of compounds vary greatly in their air sensitivity, and the misconception that it is trivial or even easy for a novice chemist to attempt a seemingly straightforward synthesis can have disastrous results. To simplify the task, we have previously developed a methodology that uses benchtop intermediates to access a wide variety of phosphine oxides (an immediate precursor to phosphines). This synthetic approach saves the air-free handling until the last step (reduction to and isolation of the phosphine). Presented herein is a complete general procedure for the facile reduction of phosphonates, phosphinates, and phosphine oxides to primary, secondary, and tertiary phosphines using aluminum hydride reducing agents. The electrophilic reducing agents (ⁱBu)₂AlH and AlH₃ were determined to be vastly superior to LiAlH₄ for reduction selectivity and reactivity. Notably, it was determined that AlH₃ is capable of reducing the exceptionally resistant tricyclohexylphosphine oxide, even though LiAlH₄ and (ⁱBu)₂AlH were not. Using this new procedure, gram-scale reactions to synthesize a representative range of primary, secondary, and tertiary phosphines (including volatile phosphines) were achieved reproducibly with excellent yields and unmatched purity without the need for a purification step.

中文翻译：

一级，二级和三级膦的革兰氏级合成的通用方法

尽管有机膦的合成在一个世纪的上半叶已广为人知，但是即使对于资深的合成化学家来说，膦的合成仍然代表着艰巨的任务。膦作为一类化合物，其对空气的敏感性差异很大，并且误以为新手化学家尝试看似简单的合成是微不足道的，甚至是容易的，这会带来灾难性的结果。为了简化任务，我们之前已经开发出一种使用台式中间体访问各种氧化膦（膦的直接前体）的方法。这种合成方法可以节省无空气的处理，直到最后一步（还原并分离出膦）。本文介绍了将膦酸酯，次膦酸酯和膦氧化物轻松还原为伯，仲，和叔膦使用氢化铝还原剂。亲电还原剂（ⁱ Bu）₂ AlH和AlH₃在还原选择性和反应性方面被确定大大优于LiAlH₄。值得注意的是，即使LiAlH₄和（ⁱ Bu）₂ AlH不能，AlH₃仍能还原具有极强抗性的三环己基氧化膦。使用这种新方法，可以以克级反应合成出代表性范围的伯，仲和叔膦（包括挥发性膦），而无需纯化步骤，可实现出色的收率和无与伦比的纯度。

更新日期：2018-01-09

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