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

Andrew J. Paterson | Zendy; Petter Dunås | Zendy; Martin Rahm | Zendy; PerOla Norrby | Zendy; Gabriele KociokKöhn | Zendy; Simon E. Lewis | Zendy; Nina Kann | Zendy

Open Access

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

Author(s) -

Andrew J. Paterson,

Petter Dunås,

Martin Rahm,

PerOla Norrby,

Gabriele KociokKöhn,

Simon E. Lewis,

Nina Kann

Publication year - 2020

Publication title -

organic letters

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.94

H-Index - 239

eISSN - 1523-7060

pISSN - 1523-7052

DOI - 10.1021/acs.orglett.0c00708

Subject(s) - chemistry , stereocenter , stereoselectivity , chirality (physics) , catalysis , benzoic acid , palladium , stereochemistry , kinetic resolution , ketone , enantioselective synthesis , combinatorial chemistry , organic chemistry , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model

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.

The content you want is available to Zendy users.

Already have an account? Click here to sign in.

Having issues? You can contact us here

Accelerating Research