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Transition Metal Catalyzed [π2s + π2s + σ2s + σ2s] Pericyclic Reaction: Woodward–Hoffmann Rules, Aromaticity, and Electron Flow

Cusumano, Alexander Q. and Goddard, William A., III and Stoltz, Brian M. (2020) Transition Metal Catalyzed [π2s + π2s + σ2s + σ2s] Pericyclic Reaction: Woodward–Hoffmann Rules, Aromaticity, and Electron Flow. Journal of the American Chemical Society, 142 (45). pp. 19033-19039. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20201028-103039420

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Abstract

We have shown that the fundamental step responsible for enantioinduction in the inner-sphere asymmetric Tsuji allylic alkylation is C–C bond formation through a seven-membered pericyclic transition state. We employ an extensive series of quantum mechanics (QM) calculations to delineate how the electronic structure of the Pd-catalyzed C–C bond forming process controls the reaction. Phase inversion introduced by d orbitals renders the Pd-catalyzed [π2s + π2s + σ2s + σ2s] reaction symmetry-allowed in the ground state, proceeding through a transition state with Craig–Möbius-like σ-aromaticity. Lastly, we connect QM to fundamental valence bonding concepts by deriving an ab initio “arrow-pushing” mechanism that describes the flow of electron density through the reaction.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.0c09575DOIArticle
ORCID:
AuthorORCID
Cusumano, Alexander Q.0000-0002-2914-2008
Goddard, William A., III0000-0003-0097-5716
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2020 American Chemical Society. Received: September 6, 2020; Published: October 27, 2020. We thank Professor Kendall Houk (UCLA) for insightful discussion. The Caltech High Performance Computing (HPC) center is acknowledged for support of computational resources. We thank the NIH (R01 GM080269), NSF (CBET-1805022), NSF (CBET-2005250), and Caltech for financial support. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01 GM080269
NSFCBET-1805022
NSFCBET-2005250
CaltechUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1394
Issue or Number:45
Record Number:CaltechAUTHORS:20201028-103039420
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20201028-103039420
Official Citation:The Transition Metal Catalyzed [π2s + π2s + σ2s + σ2s] Pericyclic Reaction: Woodward–Hoffmann Rules, Aromaticity, and Electron Flow. Alexander Q. Cusumano, William A. Goddard, and Brian M. Stoltz. Journal of the American Chemical Society 2020 142 (45), 19033-19039; DOI: 10.1021/jacs.0c09575
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106327
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Oct 2020 18:27
Last Modified:27 Nov 2020 20:14

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