Development of Enantioselective Palladium-Catalyzed Alkene Carboalkoxylation Reactions for the Synthesis of Tetrahydrofurans

• Published in: Angewandte Chemie International Edition Vol. 54; no. 45; pp. 13390 - 13392
• Main Authors: Hopkins, Brett A., Garlets, Zachary J., Wolfe, John P.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 02.11.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes - chemistry; Aromatic compounds; asymmetric catalysis; Bromides; Catalysis; Chemical reactions; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Enantiomers; enantioselective synthesis; Enrichment; Furans - chemical synthesis; Furans - chemistry; heterocycles; Inorganic salts; Ligands; Molecular Structure; Organometallic Compounds - chemistry; Palladium; Palladium - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; Tetrahydrofuran; Transformations; enantioselective synthesis; ALCOHOLS; INSERTION; heterocycles; CARBOETHERIFICATION; palladium; ARYL; asymmetric catalysis; STEREOSELECTIVE-SYNTHESIS; FUSED-RING; ACETOGENINS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201506884

The Pd‐catalyzed coupling of γ‐hydroxyalkenes with aryl bromides affords enantiomerically enriched 2‐(arylmethyl)tetrahydrofuran derivatives in good yield and up to 96:4 e.r. This transformation was achieved through the development of a new TADDOL/2‐arylcyclohexanol‐derived chiral phosphite ligand. The transformations are effective with an array of different aryl bromides, and can be used for the preparation of products bearing quaternary stereocenters. The construction of enantiomerically enriched tetrahydrofurans is accomplished by asymmetric Pd‐catalyzed cross‐coupling reactions between γ‐hydroxyalkenes and aryl bromides. Use of a palladium catalyst supported by a new TADDOL‐derived chiral phosphite ligand provides the tetrahydrofuran products in good yield with up to 96:4 e.r. (see scheme).