Enantioselective Michael Spirocyclization of Palladium Enolates.

07 March 2025, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

ABSTRACT: We report an enantio- and diastereoselective Michael spirocyclization reaction of tetrasubstituted palladium enolates. This allows for the formation of adjacent all-carbon quaternary and tertiary stereocenters in good yield, dr, and ee. Various subsequent cyclization reactions enable access to a diverse range of tricyclic scaffolds. The mechanism of this trans-formation is evaluated via quantum mechanics calculations to elucidate the origins of stereoselectivity and the mechanism of catalyst turnover.

Keywords

asymmetric catalysis
palladium catalysis
Michael cyclizations
quantum mechanics calculations

Supplementary materials

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Supporting Information
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experimental procedures and spectra
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X-Ray Files
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cif files of X-ray structures
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QM_Energies
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Computational: Quantum mechanical energies
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computed structures
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computed structures
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