Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes: Chirality Transfer via a Heck-Type Mechanism

Andrew J. Paterson, Petter Dunås, Martin Rahm, Per Ola Norrby, Gabriele Kociok-Köhn, Simon E. Lewis, Nina Kann

Research output: Contribution to journalArticle

Abstract

Microbial arene oxidation of benzoic acid with Ralstonia eutropha B9 provides a chiral highly functionalized cyclohexadiene, suitable for further structural diversification. Subjecting this scaffold to a Pd-catalyzed Heck reaction effects a regio- and stereoselective arylation of the cyclohexadiene ring, with 1,3-chirality transfer of stereogenic information installed in the microbial arene oxidation. Quantum chemical calculations explain the selectivity both by a kinetic preference for the observed arylation position and by reversible carbopalladation in competing positions. Further product transformation allowed the formation of a tricyclic ketone possessing four stereogenic centers. This demonstrates the capability of the method to introduce stereochemical complexity from planar nonchiral benzoic acid in just a few steps.

Original languageEnglish
Pages (from-to)2464-2469
Number of pages6
JournalOrganic Letters
Volume22
Issue number6
Early online date9 Mar 2020
DOIs
Publication statusPublished - 20 Mar 2020

ASJC Scopus subject areas

  • Materials Science(all)

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