A Biomimetic Synthesis of (+/-)-Basiliolide B

A highly diastereoselective and practical biomimetic total synthesis of (+/-)-basiliolideB has been achieved through the study of the two proposed biosynthetic pathways (O-methylation and O-acylation) for the unprecedented 7-methoxy-4,5-dihydro-3H-oxepin-2-one (Cring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2-pyrone Diels-Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O-acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7-membered acyl ketene acetal moiety of the Cring.http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000343751100033&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701Chemistry, MultidisciplinarySCI(E)EIPubMed8ARTICLElizc@pkusz.edu.cn4211294-112975