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Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles.

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.

SUBMITTER: Trost BM

PROVIDER: S-EPMC8356815 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Palladium-catalyzed asymmetric allylic alkylation (AAA) with alkyl sulfones as nucleophiles.

Trost Barry M BM Jiao Zhiwei Z Gholami Hadi H

Chemical science 20210702 31

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 <i>in situ</i> generated α-sulfonyl carbon anion was quickly captured by the allylic intermediates, afford ...[more]

PMID: 34447546

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