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A Biomimetic Synthesis of (±)‐Basiliolide B
Author(s) -
Min Long,
Zhang Yang,
Liang Xuefeng,
Huang Junrong,
Bao Wenli,
Lee ChiSing
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201405770
Subject(s) - stereocenter , cycloaddition , moiety , ring (chemistry) , total synthesis , biomimetic synthesis , chemistry , intramolecular force , ketene , acetal , stereochemistry , cyclopropanation , acylation , enantioselective synthesis , organic chemistry , catalysis
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 H ‐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.