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Synthesis of (+)‐Obtusenyne
Author(s) -
Mak S. Y. Frankie,
Curtis Neil R.,
Payne Andrew N.,
Congreve Miles S.,
Wildsmith Andrew J.,
Francis Craig L.,
Davies John E.,
Pascu Sofia I.,
Burton Jonathan W.,
Holmes Andrew B.
Publication year - 2008
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.200701567
Subject(s) - enantioselective synthesis , intramolecular force , chemistry , ring (chemistry) , ether , ketene , acetal , enol ether , stereochemistry , williamson ether synthesis , total synthesis , enol , silyl enol ether , dioxolane , claisen rearrangement , tetrahydropyran , combinatorial chemistry , catalysis , medicinal chemistry , organic chemistry
An enantioselective synthesis of the halogenated medium‐ring ether natural product (+)‐obtusenyne is reported which uses the ring expansion of a seven‐membered ketene acetal by means of a Claisen rearrangement to construct the core nine‐membered oxygen heterocycle. The trans substituents across the ether linkage were established by using a transition‐metal‐catalyzed intramolecular hydrosilation reaction of an exo ‐cyclic enol ether. In addition, a formal synthesis of ent ‐obtusenyne from 2‐deoxy‐ D ‐ribose is reported. A number of interesting points regarding the chemistry of medium‐ring oxygen heterocycles are highlighted.