Chiral Ligands Based on Binaphthyl Scaffolds for Pd-Catalyzed Enantioselective C–H Activation/Cycloaddition Reactions

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2022_JACS_GONZALEZ_CHIRAL.pdf (2.1 MB)
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URI: http://hdl.handle.net/10347/29687
ISSN: 0002-7863
E-ISSN: 1520-5126
DOI: 10.1021/jacs.2c09479

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2022

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ACS Publications
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Abstract

We report the first examples of the use of a new class of ligands (NOBINAc) for performing asymmetric C–H activations using palladium catalysts. These ligands combine the axial chirality of binaphthyl scaffolds with the bifunctional and bidentate coordination properties of mono-N-protected amino acids (MPAAs), which are well-known to favor Pd-promoted C–H activations via concerted metalation–deprotonation mechanisms. We demonstrate that our new ligands enable substantially higher enantioselectivities than MPAAs in the assembly of 2-benzazepines through formal (5 + 2) cycloadditions between homobenzyltriflamides or o-methylbenzyltriflamides and allenes

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Allenes| Annulations| Chemical structure| Ligands| Stereoselectivity

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J. Am. Chem. Soc. 2022, 144, 47, 21437–21442

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This work received financial support from the MCIN/AEI/10.13039/501100011033 (Projects PID2019-108624RB-I00, PID2019-110385GB-I00, and PID2020-119116RA-I00 and FPU Fellowship to X.V.), the Consellería de Cultura, Educación e Ordenación Universitaria (ED431C-2021/25, ED431G 2019/03: Centro Singular de Investigación de Galicia accreditation 2019–2022, and fellowship to J.M.G.), and the European Regional Development Fund (ERDF). The orfeo-cinqa network CTQ2016-81797-REDC is also kindly acknowledged. M.A.O. acknowledges the Xunta Distinguished Researcher Program (ED431H 2020/21) for funding and Centro de Supercomputación de Galicia (CESGA) for providing generous computational resources. Figures were created with CYLview20

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© 2022 The Authors. Published by American Chemical Society. This work is under a CC Attribution 4.0 International (CC BY 4.0)
Atribución 4.0 Internacional

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Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Química Orgánica