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Nitrosobenzene: Reagent for the Mitsunobu Esterification Reaction.

ABSTRACT: 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.

SUBMITTER: Pokluda A

PROVIDER: S-EPMC6648318 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Nitrosobenzene: Reagent for the Mitsunobu Esterification Reaction.

Pokluda Adam A Kohout Michal M Chudoba Josef J Krupička Martin M Cibulka Radek R

ACS omega 20190307 3

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 u ...[more]

PMID: 31459682

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