化学
二苯基氧化膦
SN2反应
催化作用
光延反应
氧化膦
磷化氢
亲核细胞
氧化还原
催化循环
分子内力
氧化物
药物化学
组合化学
有机化学
作者
Yike Zou,Jonathan J. Wong,K. N. Houk
摘要
The mechanism of the redox-neutral organocatalytic Mitsunobu reaction, catalyzed by (2-hydroxybenzyl)diphenylphosphine oxide, reported by Denton et al., has been studied computationally with ωB97X-D density functional theory. We discovered that the nucleophilic substitution reaction between carboxylate and alkoxyphosphonium 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.
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