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Updated: Jan 28, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Umpolung Reactivity of in Situ Generated Phosphido-Boranes: An Entry to P-Stereogenic Aminophosphine-Boranes
Sébastien Lemouzy1, Romain Membrat1, Enzo Olivieri1
1Aix Marseille Univ, CNRS, Centrale Marseille, iSm2 , Marseille 13397 , France.
Abstract:
The synthesis of P-stereogenic aminophosphine-boranes has been developed on the basis of umpolung reactivity of in situ generated alkylarylphosphido-boranes, which are normally configurationally unstable intermediates. In our case, their high configurational stability was due to the slow release of the hydroxyalkyl protecting group, together with the fast formation of the iodophosphanylborane in the presence of N-iodosuccinimide. The subsequent substitution reaction was found to proceed in moderate to good yields and in a very high stereospecifity (es) using a variety of amines as nucleophiles.
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