Asymmetric total synthesis of (-)-plicatic acid via a highly enantioselective and diastereoselective nucleophilic epoxidation of acyclic trisubstitued olefins.
The first total synthesis of (-)-plicatic acid has been achieved by a concise and enantioselective route. In this synthesis, a conceptually new strategy featuring an asymmetric epoxidation-intramolecular epoxy-ring-opening Friedel-Crafts reaction sequence was developed for the stereoselective construction of the 2,7'-cyclolignane skeleton bearing contiguous quaternary-quaternary-tertiary stereocenters. The implementation of this strategy was enabled by the development of a modified protocol for the Seebach epoxidation with TADOOH, which affords an unprecedented, highly enantioselective and diastereoselective epoxidation with a range of alpha-carbonyl-beta-substituted acrylates 3.
Sun
Bing-Feng
BF
Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02454-9110, USA.
Hong
Ran
R
Kang
Yan-Biao
YB
Deng
Li
L
D000475:Alkenes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D017705:Lignans / Q000138:chemical synthesis* / Q000737:chemistry*; D009284:Naphthols / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D000475:Alkenes; D004852:Epoxy Compounds; D017705:Lignans; D009284:Naphthols; C008938:plicatic acid