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Asymmetric Total Syntheses and Structure Confirmation of Chlorofucins and Bromofucins
Author(s) -
Kim Byungsook,
Sohn Teik,
Kim Deukjoon,
Paton Robert S.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704564
Subject(s) - electrophile , intramolecular force , chemistry , metathesis , stereochemistry , alcohol , total synthesis , salt metathesis reaction , substrate (aquarium) , organic chemistry , catalysis , biology , ecology , polymer , polymerization
Abstract Substrate‐controlled asymmetric total syntheses and structure confirmation of (+)‐(3 E )‐ and (−)‐(3 Z )‐chlorofucin [( E )‐ 1 a and ( Z )‐ 1 a ], and (+)‐(3 E )‐ and (−)‐(3 Z )‐bromofucin [( E )‐ 1 b and ( Z )‐ 1 b ] were accomplished. Our syntheses feature as key steps haloetherification (either ‘conventional’ or ‘one‐pot organoselenium‐mediated’) of α,α′‐ trans ‐γ,δ‐unsaturated oxocene alcohol 9 and our ( E )‐ and ( Z )‐selective cross‐metathesis (CM) protocols. More importantly, a rationale is provided for the strikingly different pathways followed by α,α′‐ trans ‐γ,δ‐unsaturated oxocene alcohol 9 and its α,α′‐ cis isomer 9′ in the presence of different electrophiles during the intramolecular electrophilic addition reactions.