Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System

Joseph A. Buonomo, Courtney C. Aldrich

Research output: Contribution to journalArticlepeer-review

78 Scopus citations

Abstract

The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction. Make it catalytic: A catalytic Mitsunobu reaction using innocuous reagents to recycle the stoichiometric phosphine oxide and hydrazine by-products was developed. The reported method is catalytic in 1-phenylphospholane and uses phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction.

Original languageEnglish (US)
Pages (from-to)13041-13044
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number44
DOIs
StatePublished - Oct 1 2015

Bibliographical note

Publisher Copyright:
© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Keywords

  • organocatalysis
  • phosphorus heterocycles
  • reaction kinetics
  • silanes
  • synthetic methods

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