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Nickel-catalyzed switchable 1,3-dienylation and enantioselective allenylation of phosphine oxides.

ABSTRACT: The development of general catalytic methods for the regio- and stereoselective construction of phosphoryl derivatives from identical substrates remains a formidable challenge in organic synthesis. Enabled by the newly developed BDPP-type ligands, we disclosed a nickel-catalyzed allenylation of phosphine oxides rationally and predictably, allowing the construction of versatile chiral allenylphosphoryl derivatives with high enantiopurity (up to 94% e.e.). Alternatively, using an achiral phosphine ligand dcypbz under acidic conditions, we achieved a regiochemical switch of the 1,3-dienylation to afford functionalized phosphinoyl 1,3-butadienes (up to 93% yield). The salient features of this method include switchable reactivity, broad substrate scope, readily available feedstock, single-step preparation, and high asymmetric induction.

SUBMITTER: Zhang J

PROVIDER: S-EPMC9671958 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Nickel-catalyzed switchable 1,3-dienylation and enantioselective allenylation of phosphine oxides.

Zhang Jiayin J Chang Xihao X Xu Xianghong X Wang Hongyi H Peng Lingzi L Guo Chang C

Nature communications 20221117 1

The development of general catalytic methods for the regio- and stereoselective construction of phosphoryl derivatives from identical substrates remains a formidable challenge in organic synthesis. Enabled by the newly developed BDPP-type ligands, we disclosed a nickel-catalyzed allenylation of phosphine oxides rationally and predictably, allowing the construction of versatile chiral allenylphosphoryl derivatives with high enantiopurity (up to 94% e.e.). Alternatively, using an achiral phosphine ...[more]

PMID: 36396661

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