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. 2019 Jul 31;141(30):11864-11869.
doi: 10.1021/jacs.9b06366. Epub 2019 Jul 16.

Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes

Honghui Lei  1 , John H Conway Jr  1 , Caleb C Cook  1 , Tomislav Rovis  1
Affiliations

Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes

Honghui Lei et al. J Am Chem Soc. .

Abstract

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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Alkene Oxyamination
Scheme 2.
Scheme 2.. γ-Lactam Scopea
aConditions: 1 (0.1 mmol, 1.0 equiv), 2 or ZnX2 (2.5 equiv), [Cp*Ir(CH3CN)3]2(SbF6)2 (5 mol%), K2CO3 (20 mol%), HFIP (0.3 M), 30 °C for 16 h. b1.0 equiv K2CO3. c40 °C. dFrom E-olefin; eFrom Z-olefin; f4°C.
Scheme 3.
Scheme 3.. Amino Lactone Scopea
aConditions: 1 (0.1 mmol, 1.0 equiv), BocNHOPiv (1.5 equiv), [Cp*pCF3IrCl2]2 (2.5 mol%), NaOPiv (1.0 equiv), HFIP (0.3 M), 40 °C for 16 h. b5 mol% of [Cp*pCF3IrCl2]2. c5 mol% of [Cp*sdpCF3IrCl2]2.
Scheme 4.
Scheme 4.. δ-Lactam Scopea
aConditions: 1 (0.1 mmol, 1.0 equiv), 2 (2.5 equiv), [Cp*pCF3Ir(CH3CN)3]2(SbF6)2 (5 mol%), CsOPiv (20 mol%), HFIP (0.3 M), 30 °C for 16 h. b24 °C. c2.5 mol% [Cp*sdpCF3Ircl2]2 used. d1.0 equiv CsOPiv used. e40 °C. fThe relative stereochemistry was determined via NOESY analysis.
Scheme 5.
Scheme 5.
Mechanistic Studies
See this image and copyright information in PMC

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