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, 31P NMR spectroscopy, and experiments conducted with isotopically labeled substrates.

Department of Organic Chemistry and Central Laboratories University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

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