A Biomimetic Synthesis of (±)‐Basiliolide B1. Issue 42 (27th August 2014)

• Record Type: Journal Article
• Authors: Min, Long; Zhang, Yang; Liang, Xuefeng; Huang, Junrong; Bao, Wenli; Lee, Chi‐Sing
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 42(2014)
• Page Start: 11294
• Page End: 11297
• Publication Date: 2014-08-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201405770
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A highly diastereoselective and practical biomimetic total synthesis of (±)‐basiliolide B 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‐3<italic>H</italic>‐oxepin‐2‐one (C ring). 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 C ring.</p> </abstract>