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Stereoselective Substrate‐Controlled Asymmetric Syntheses of both 2,5‐ cis ‐ and 2,5‐ trans ‐Tetrahydrofuranoid Oxylipids: Stereodivergent Intramolecular Amide Enolate Alkylation
Author(s) -
Jang Hongjun,
Shin Iljin,
Lee Dongjoo,
Kim Hyoungsu,
Kim Deukjoon
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201600637
Subject(s) - stereoselectivity , chemistry , intramolecular force , amide , alkylation , tetrahydrofuran , stereochemistry , enantioselective synthesis , substrate (aquarium) , organic chemistry , catalysis , oceanography , solvent , geology
The concise, highly stereoselective, substrate‐controlled asymmetric total syntheses of both 2,5‐cis‐ and 2,5‐trans‐tetrahydrofuranoid nematocidal oxylipids from the Australian brown algae Notheia anomala have been accomplished in a stereodivergent fashion. The highly stereoselective intramolecular amide enolate alkylation strategy provides access to both stereoisomers of the 3‐hydroxy‐2,5‐disubstituted tetrahydrofuran core of these marine natural products through chelate and nonchelate control, which is driven by the C3‐hydroxy protecting group. This approach offers an optional and highly stereoelective access to any of the eight possible stereoisomers of the 2,5‐disubstituted‐3‐oxygenated tetrahydrofuran skeleton, an important structural feature which is present in many biologically active natural products.