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Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes.

ABSTRACT: An intramolecular Ir(III)-catalyzed regiodivergent oxyamination of unactivated alkenes provides valuable ?-lactams, ?-lactones and ?-lactams. The regioselectivity is controlled by the electronically tunable cyclopentadienyl Ir(III)-complexes enabling oxyamination via either 5-exo or 6-endo pathways. With respect to the mechanism, we propose a highly reactive [3.1.0] bicycle intermediate derived from Ir(V) nitrene-mediated aziridination to be a key intermediate toward the synthesis of ?-lactams.

SUBMITTER: Lei H

PROVIDER: S-EPMC6980349 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes.

Lei Honghui H Conway John H JH Cook Caleb C CC Rovis Tomislav T

Journal of the American Chemical Society 20190716 30

An intramolecular Ir(III)-catalyzed regiodivergent oxyamination of unactivated alkenes provides valuable γ-lactams, γ-lactones and δ-lactams. The regioselectivity is controlled by the electronically tunable cyclopentadienyl Ir(III)-complexes enabling oxyamination via either 5-exo or 6-endo pathways. With respect to the mechanism, we propose a highly reactive [3.1.0] bicycle intermediate derived from Ir(V) nitrene-mediated aziridination to be a key intermediate toward the synthesis of γ-lactams. ...[more]

PMID: 31310537

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