title: Gold(I)-Catalyzed Desymmetrization of 1,4-Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement.
abstract: An enantioselective alkoxylation/Claisen rearrangement reaction was achieved by a strategic desymmetrization of 1,4-dienes under the catalysis of (S)-DTBM-Segphos(AuCl)2/AgBF4. This reaction system was highly selective for the formation of 3,3-rearrangement products, providing cycloheptenes with various substitutions in good yield and good to excellent enantioselectivity. This transformation was further extended to bicyclic ring substrates, providing the opportunity to easily assemble 5,6- and 6,7-fused ring systems.
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA).|Institute of Chemistry and BioMedical Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China).
authors.forename: Hongmiao
authors.initials: H
authors.lastname: Wu
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA).
authors.forename: Weiwei
authors.initials: W
authors.lastname: Zi
authors.affiliation: Institute of Chemistry and BioMedical Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China).
authors.forename: Guigen
authors.initials: G
authors.lastname: Li
authors.affiliation: Institute of Chemistry and BioMedical Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China). hongjianlu@nju.edu.cn.
authors.forename: Hongjian
authors.initials: H
authors.lastname: Lu
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA). fdtoste@berkeley.edu.
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D002384:Catalysis; D003508:Cycloheptanes / Q000138:chemical synthesis* / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D011090:Polyenes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D003508:Cycloheptanes; D011090:Polyenes; D006046:Gold
keywords: Claisen rearrangement; alkoxylation; desymmetrization; enantioselectivity; gold