Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

Chetan C. Chintawar; Vivek W. Bhoyare; Manoj Vasisht Mane; Nitin T. Patil

doi:10.1021/jacs.2c02799

Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

Chetan C. Chintawar, Vivek W. Bhoyare, Manoj Vasisht Mane, Nitin T. Patil

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity

Original language	English (US)
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.2c02799
State	Published - Apr 18 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-04-21
Acknowledgements: Generous financial support by the Science and Engineering Research Board (SERB), New Delhi (File Nos. DIA/2018/000016 and EMR/2016/007177), is gratefully acknowledged. C.C.C. and V.W.B. thank the UGC and CSIR, respectively, for the award of Senior Research Fellowships. We thank Abhik Paul from IISERB for his assistance with SC-XRD analysis.

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

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10.1021/jacs.2c02799

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title = "Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands",

abstract = "Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity",

author = "Chintawar, {Chetan C.} and Bhoyare, {Vivek W.} and Mane, {Manoj Vasisht} and Patil, {Nitin T.}",

note = "KAUST Repository Item: Exported on 2022-04-21 Acknowledgements: Generous financial support by the Science and Engineering Research Board (SERB), New Delhi (File Nos. DIA/2018/000016 and EMR/2016/007177), is gratefully acknowledged. C.C.C. and V.W.B. thank the UGC and CSIR, respectively, for the award of Senior Research Fellowships. We thank Abhik Paul from IISERB for his assistance with SC-XRD analysis.",

year = "2022",

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doi = "10.1021/jacs.2c02799",

language = "English (US)",

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T1 - Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

AU - Chintawar, Chetan C.

AU - Bhoyare, Vivek W.

AU - Mane, Manoj Vasisht

AU - Patil, Nitin T.

N1 - KAUST Repository Item: Exported on 2022-04-21 Acknowledgements: Generous financial support by the Science and Engineering Research Board (SERB), New Delhi (File Nos. DIA/2018/000016 and EMR/2016/007177), is gratefully acknowledged. C.C.C. and V.W.B. thank the UGC and CSIR, respectively, for the award of Senior Research Fellowships. We thank Abhik Paul from IISERB for his assistance with SC-XRD analysis.

PY - 2022/4/18

Y1 - 2022/4/18

N2 - Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity

AB - Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity

UR - http://hdl.handle.net/10754/676330

UR - https://pubs.acs.org/doi/10.1021/jacs.2c02799

U2 - 10.1021/jacs.2c02799

DO - 10.1021/jacs.2c02799

M3 - Article

C2 - 35436097

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

Abstract

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