The mechanism of the redox-neutral organocatalytic Mitsunobu reac-tion, catalyzed by (2-hydroxybenzyl)diphenylphosphine oxide, re-ported by Denton et al., has been studied computationally with ωB97X-D density functional theory. We discovered that the nucleo-philic substitution reaction between carboxylate and alkoxyphospho-nium ions, to reform the phosphine oxide catalyst, is the rate-determining step of the overall process and is significantly accelerated compared with a general-acid-catalyzed SN2 reaction. The (2-hydroxybenzyl)diphenylphosphine oxide is regenerated and activated in every catalytic cycle via intramolecular dehydration/cyclization. We also designed several phosphine oxide catalysts that we predict to be more effective catalysts.

中文翻译：

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氧化还原中性有机催化光信反应的计算探索

Denton 等人报道的由（2-羟基苄基）二苯基氧化膦催化的氧化还原-中性有机催化的 Mitsunobu 反应的机理已经用 ωB97X-D 密度泛函理论进行了计算研究。我们发现，羧酸盐和烷氧基磷离子之间的亲核取代反应可以重整氧化膦催化剂，是整个过程的决速步骤，与一般酸催化的 SN2 反应相比，速度显着加快。(2-羟基苄基)二苯基氧化膦通过分子内脱水/环化在每个催化循环中再生和活化。我们还设计了几种氧化膦催化剂，我们预测它们是更有效的催化剂。