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

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...

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Published inOrganic letters Vol. 22; no. 6; pp. 2464 - 2469
Main Authors Paterson, Andrew J, Dunås, Petter, Rahm, Martin, Norrby, Per-Ola, Kociok-Köhn, Gabriele, Lewis, Simon E, Kann, Nina
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 20.03.2020
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
BENZOIC-ACID
DIHYDROXYLATION
GLYCALS
METABOLISM
BOND
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Summary: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.
Bibliography:Swedish Research Council
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ISSN:1523-7060
1523-7052
1523-7052
DOI:10.1021/acs.orglett.0c00708