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Palladium-Catalyzed Cross-Coupling of α-Bromocarbonyls and Allylic Alcohols for the Synthesis of α-Aryl Dicarbonyl Compounds.

ABSTRACT: The palladium-catalyzed coupling of olefins and organohalides is a versatile approach for synthesizing complex molecules from simple starting materials. We have developed a palladium-catalyzed coupling of α-bromocarbonyl compounds with allylic alcohols for the generation of acyclic aryl-substituted dicarbonyl compounds. The reaction proceeds via a tandem olefin insertion of an α-acyl radical followed by a 1,2-aryl migration. In addition to providing preliminary evidence for a free radical mediated mechanism, we demonstrate unprecedented levels of 1,3-stereoinduction for the 1,2-migration step.

SUBMITTER: Yu Y

PROVIDER: S-EPMC4516158 | biostudies-literature | 2015

REPOSITORIES: biostudies-literature

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Palladium-Catalyzed Cross-Coupling of α-Bromocarbonyls and Allylic Alcohols for the Synthesis of α-Aryl Dicarbonyl Compounds.

Yu Yang Y Tambar Uttam K UK

Chemical science 20150101

The palladium-catalyzed coupling of olefins and organohalides is a versatile approach for synthesizing complex molecules from simple starting materials. We have developed a palladium-catalyzed coupling of α-bromocarbonyl compounds with allylic alcohols for the generation of acyclic aryl-substituted dicarbonyl compounds. The reaction proceeds via a tandem olefin insertion of an α-acyl radical followed by a 1,2-aryl migration. In addition to providing preliminary evidence for a free radical mediat ...[more]

PMID: 26229586

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