Nitrosobenzene: Reagent for the Mitsunobu Esterification Reaction

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Aug 29

PMID 31459682

Citations 1

Authors

Adam Pokluda

Michal Kohout

Josef Chudoba

Martin Krupicka

Radek Cibulka

Affiliations

Soon will be listed here.

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

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PMID: 37152581 PMC: 10162371. DOI: 10.1039/d3ra02468g.

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