Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes: Chirality Transfer via a Heck-Type Mechanism
Journal article, 2020

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.

Author

Andrew Paterson

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Petter Dunås

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry, Physical Chemistry

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Per-Ola Norrby

AstraZeneca AB

G. Kociok-Köhn

University of Bath

Simon E. Lewis

University of Bath

Nina Kann

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry, Physical Chemistry

Organic Letters

1523-7060 (ISSN) 1523-7052 (eISSN)

Vol. 22 6 2464-2469

Subject Categories

Biochemistry and Molecular Biology

Biocatalysis and Enzyme Technology

Organic Chemistry

DOI

10.1021/acs.orglett.0c00708

More information

Latest update

2/19/2021