title: Asymmetric synthesis of alpha-substituted aldehydes by Pd-catalyzed asymmetric allylic alkylation-alkene isomerization-Claisen rearrangement.
abstract: [Structure: see text] Enantiospecific aliphatic Claisen rearrangement was realized with generally high chirality transfer. The requisite substrates were synthesized via Pd-catalyzed asymmetric allylic alkylation (AAA) from easily obtained starting materials. After protection, the resultant bisallyl ethers underwent olefin isomerization and in situ Claisen rearrangement (ICR) to generate alpha-chiral aldehydes. Remarkable chemoselectivity in the olefin isomerization step was observed. An asymmetric synthesis of communiol A was accomplished applying this methodology.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
authors.forename: Barry M
authors.initials: BM
authors.lastname: Trost
authors.forename: Ting
authors.initials: T
authors.lastname: Zhang
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D002384:Catalysis; D007536:Isomerism; D010165:Palladium / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D010165:Palladium