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Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes: Chirality Transfer via a Heck-Type Mechanism
- Source :
- Paterson, A J, Dunås, P, Rahm, M, Norrby, P O, Kociok-Köhn, G, Lewis, S E & Kann, N 2020, ' Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes : Chirality Transfer via a Heck-Type Mechanism ', Organic Letters, vol. 22, no. 6, pp. 2464-2469 . https://doi.org/10.1021/acs.orglett.0c00708
- Publication Year :
- 2020
- Publisher :
- American Chemical Society (ACS), 2020.
-
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 palladium-catalyzed Heck reaction effects a regioselective and stereoselective arylation of the cyclohexadiene ring. The arylation proceeds with a highly selective 1,3-chirality transfer of stereogenic information installed in the microbial arene oxidation. Quantum chemical calculations have provided insightinto the mechanism of the palladium catalyzed arylation. The high selectivity can be explained both by a kinetic preference for the observed arylation position and, interestingly, by reversible carbopalladation in competing positions. Functional groups that were well tolerated on the diene substrate included a range of esters, amides and a Weinreb amide, affording a total of 23 different productsin good yields. These products, which can be considered as latent enolic nucleophiles, also possess a unique three dimensional structure which can be utilized in further stereoselective transformations. This was demonstrated by subjecting one of the products, which contained a protected aldehyde, to a tandem deprotection – cyclization sequence. The reaction proceeded with complete stereoselectivityand afforded a tricyclic ketone product possessing four stereogenic centers. This demonstrates the capability of the method to introduce stereochemical complexity from a planar molecule such as benzoic acid in just a few steps.
- Subjects :
- Ketone
Diene
chemistry.chemical_element
010402 general chemistry
01 natural sciences
Biochemistry
Benzoates
Catalysis
Stereocenter
chemistry.chemical_compound
Materials Science(all)
Heck reaction
Cyclohexenes
Physical and Theoretical Chemistry
Benzoic acid
chemistry.chemical_classification
010405 organic chemistry
Iodobenzenes
Organic Chemistry
Stereoisomerism
Combinatorial chemistry
0104 chemical sciences
chemistry
Stereoselectivity
Cupriavidus necator
Chirality (chemistry)
Oxidation-Reduction
Palladium
Subjects
Details
- Database :
- OpenAIRE
- Journal :
- Paterson, A J, Dunås, P, Rahm, M, Norrby, P O, Kociok-Köhn, G, Lewis, S E & Kann, N 2020, ' Palladium Catalyzed Stereoselective Arylation of Biocatalytically Derived Cyclic 1,3-Dienes : Chirality Transfer via a Heck-Type Mechanism ', Organic Letters, vol. 22, no. 6, pp. 2464-2469 . https://doi.org/10.1021/acs.orglett.0c00708
- Accession number :
- edsair.doi.dedup.....bb080e9bf5db302e54971243ec9efb74