Pokluda Adam, Kohout Michal, Chudoba Josef, Krupička Martin, Cibulka Radek
Department of Organic Chemistry and Central Laboratories, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague, Czech Republic.
ACS Omega. 2019 Mar 7;4(3):5012-5018. doi: 10.1021/acsomega.8b03551. eCollection 2019 Mar 31.
Nitrosobenzene has been demonstrated to participate in the Mitsunobu reaction in an analogous manner to dialkyl azodicarboxylates. The protocol using nitrosobenzene and triphenylphosphine (1:1) under mild conditions (0 °C) provides the ester derivatives of aliphatic and aromatic acids using various alcohols in moderate yield and with good enantioselectivity, giving the desired products predominantly with an inversion of configuration. The proposed mechanism, which is analogous to that observed using dialkyl azodicarboxylates, involves a nitrosobenzene-triphenylphosphine adduct and an alkoxytriphenylphosphonium ion and was supported by density functional theory calculations, P NMR spectroscopy, and experiments conducted with isotopically labeled substrates.
已证明亚硝基苯在Mitsunobu反应中的反应方式与偶氮二甲酸二烷基酯类似。在温和条件（0°C）下使用亚硝基苯和三苯基膦（1:1）的方法，能使用各种醇以中等产率和良好的对映选择性得到脂肪族和芳香族酸的酯衍生物，主要得到构型翻转的所需产物。所提出的机理与使用偶氮二甲酸二烷基酯时观察到的机理类似，涉及亚硝基苯 - 三苯基膦加合物和烷氧基三苯基鏻离子，并且得到密度泛函理论计算、³¹P NMR光谱以及用同位素标记底物进行的实验的支持。
