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

doi:10.1021/acs.orglett.0c00708

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

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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 language	English
Pages (from-to)	2464-2469
Number of pages	6
Journal	Organic Letters
Volume	22
Issue number	6
Early online date	9 Mar 2020
DOIs	https://doi.org/10.1021/acs.orglett.0c00708
Publication status	Published - 20 Mar 2020

Funding

The Swedish Research Council (N.K., Grant 2015-05360), the Swedish Research Council Formas (N.K., Grant 2015-1106), the Engineering and Physical Sciences Research Council (S.E.L., Grant EP/L016354/1), and the Carl Trygger Foundation (A.P., Grant CTS 16:235) are gratefully acknowledged for funding. Computational resources were provided by the Swedish National Infrastructure for Computing (SNIC) at C3SE. We thank Dr. Carl Johan Wallentin, Dept. of Chemistry and Molecular Biology, University of Gothenburg, and Prof. Christer Larsson, Dept. of Biology and Biological Engineering, Chalmers University of Technology, for discussions.

ASJC Scopus subject areas

General Materials Science

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10.1021/acs.orglett.0c00708Licence: CC BY

___OL_2020_22_2464___Final published version, 2.36 MBLicence: CC BY

Cite this

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

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.",

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T1 - Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes

T2 - Chirality Transfer via a Heck-Type Mechanism

AU - Paterson, Andrew J.

AU - Dunås, Petter

AU - Rahm, Martin

AU - Norrby, Per Ola

AU - Kociok-Köhn, Gabriele

AU - Lewis, Simon E.

AU - Kann, Nina

PY - 2020/3/20

Y1 - 2020/3/20

N2 - 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.

AB - 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.

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

Abstract

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

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

MC2- X-ray diffraction (XRD)

Cite this