Asymmetric Allylic C–H Oxidation for the Synthesis of Chromans

• Published in: Journal of the American Chemical Society Vol. 137; no. 40; pp. 12732 - 12735
• Main Authors: Wang, Pu-Sheng, Liu, Peng, Zhai, Yu-Jia, Lin, Hua-Chen, Han, Zhi-Yong, Gong, Liu-Zhu
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 14.10.2015; Amer Chemical Soc
• Subjects: Catalysis; catalytic activity; Chemistry; Chemistry, Multidisciplinary; Chromans - chemical synthesis; Chromans - chemistry; enantiomers; ligands; oxidation; Oxidation-Reduction; palladium; Physical Sciences; Science & Technology; Stereoisomerism; ALCOHOLS; FUNCTIONALIZATION; ENANTIOSELECTIVE APPROACH; VITAMIN-E; SECALONIC ACIDS; ALKYLATION; ALPHA; CHIRAL CHROMANS; TERMINAL OLEFINS; TETRAHYDROXANTHONE
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.5b08477

An enantioselective intramolecular allylic C–H oxidation to generate optically active chromans has been accomplished under the cooperative catalysis of a palladium complex of chiral phosphoramidite ligand and 2-fluorobenzoic acid. Mechanistic studies suggest that this reaction commences with a Pd-catalyzed allylic C–H activation event and then undergoes asymmetric allylic alkoxylation. The synthetic significance of the method has been embodied by concisely building up a key chiral intermediate to access (+)-diversonol.