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1 digital object.

Description

ABSTRACT: Stereogenic units are a critical source of molecular complexity, but their stereoselective formation via main group ambiphiles— which are suitable for derivatizing a wide scope of functionalities—is largely unexplored. Herein, using chiral cyclic (alkyl)(amino)carbenes (ChiCAACs), we study stereoinduction during the oxidative addition of E–H σ-bonds (E = C, N, O, Si, P). Through computational modeling, the relationship between stereochemical outcome and mechanism is elucidated, providing insight into when and why ChiCAACs exhibit excellent stereoselectivities. Altogether, these results demonstrate the potential for chiral main group ambiphiles to generate stereogenic units in a highly controlled manner opening avenues for applying “metal-like” reactivity in metal-free asymmetric syntheses.

Creation Date

• 2024-05 to 2025-01

Date Issued

• 2025

Authors

• Gembicky, Milan
• Lorkowski, Jan
• Morvan, Fanny
• Morvan, Jennifer
• Roisnel, Thierry
• Vanthuyne, Nicolas
• Yorkgitis, Patrick

Principal Investigator

• Bertrand, Guy

Co Principal Investigators

• Jazzar, Rodolphe
• Mauduit, Marc

Funding

We are grateful to the French Centre National de la Recherche Scientifique (CNRS), the Ecole Nationale Supérieure de Chimie de Rennes and the University of California San Diego. This work was supported by the “Prematuration Program” of CNRS (MM), the Agence Nationale de la Recherche (ANR) under award ANR-19-CE07-0017-ChiCAAC (MM, RJ) and #ANR-20-CE07-0030-cResolu (MM, RJ). This work was supported by the NSF (CHE- 2246948) (GB). This research was supported in part by the W. M. Keck Foundation through computing resources at the W. M. Keck Laboratory for Integrated Biology.

Topics

• Carbene
• Chirality
• Cyclic(alkyl)(amino)carbenes (CAAC)
• Density functional theory (DFT)
• Diastereoselective
• Domain: Chemical sciences
• Main group
• Organic chemistry
• Oxidative addition

Format

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• data

Language

• English

Identifier

Identifier: Guy Bertrand: https://orcid.org/0000-0003-2623-2363

Identifier: Jan Lorkowski: https://orcid.org/0000-0003-3436-1296

Identifier: Jennifer Morvan: https://orcid.org/0000-0003-1210-7975

Identifier: Marc Mauduit: https://orcid.org/0000-0002-7080-9708

Identifier: Milan Gembicky: https://orcid.org/0000-0002-3898-1612

Identifier: Nicolas Vanthuyne: https://orcid.org/0000-0003-2598-7940

Identifier: Patrick Yorkgitis: https://orcid.org/0000-0002-5285-0184

Identifier: Rodolphe Jazzar: https://orcid.org/0000-0002-4156-7826

Identifier: Thierry Roisnel: https://orcid.org/0000-0002-6088-4472

Related Resources

Primary associated publication

• Lorkowski, J; Yorkgitis, P; Morvan, F; Morvan, J; Vanthuyne, N; Roisnel, T; Gembicky, M; Bertrand, G; Mauduit, M; Jazzar, R. Singlet Carbenes Are Stereoinductive Main Group Ambiphiles. J. Am. Chem. Soc. 2025, 147, 17, 14777–14784. https://doi.org/10.1021/jacs.5c03845

Related data

• Compound (R)-1: CCDC 2385238 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l215x
• Compound (R)-2: CCDC 2385855 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l2p2g
• Compound (R)-3: CCDC 2385237 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l214w
• Compound (R)-4: CCDC 2385236 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l213v
• Compound (R)-5: CCDC 2385234 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l211s
• Compound (R)-6: CCDC 2385854 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l2p1f
• Compound (R,R)-15: CCDC 2401279 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2llqmk
• Compound (R,R)-17: CCDC 2428557 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2mj3kv
• Compound (R,R)-18: CCDC 2428558 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2mj3lw
• Compound (R,R)-8: CCDC 2401280 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2llqnl
• Compound (R,S)-14: CCDC 2401282 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2llqqn
• Compound (R,S)-9: CCDC 2401281 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2llqpm
• Compound (S)-1: CCDC 2385239 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l216y
• Compound (S)-2: CCDC 2385856 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l2p3h
• Compound (S)-4: CCDC 2385235 (Cambridge Crystallographic Data Centre): https://doi.org/10.5517/ccdc.csd.cc2l212t

Reference

• Neese F. Software update: The ORCA program system—Version 5.0. WIREs Comput Mol Sci. 2022, 12:e1606. https://doi.org/10.1002/wcms.1606

Collection image

• Image credit: Rodolphe Jazzar and Jan Lorkowski. "Singlet carbenes as stereoinductive ambiphiles."