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Updated: Oct 22, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles
Barry M Trost1, Zhiwei Jiao2, Hadi Gholami1
1Departmentof Chemistry, Stanford University Stanford CA 94305-5080 USA bmtrost@stanford.edu.
Abstract:
An efficient palladium-catalyzed AAA reaction with a simple α-sulfonyl carbon anion as nucleophiles is presented for the first time. Allyl fluorides are used as superior precursors for the generation of π-allyl complexes that upon ionization liberate fluoride anions for activation of silylated nucleophiles. With the unique bidentate diamidophosphite ligand ligated palladium as catalyst, the in situ generated α-sulfonyl carbon anion was quickly captured by the allylic intermediates, affording a series of chiral homo-allylic sulfones with high efficiency and selectivity. This work provides a mild in situ desilylation strategy to reveal nucleophilic carbon centers that could be used to overcome the pK a limitation of "hard" nucleophiles in enantioselective transformations.
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