Journal article
Synthesis of ( )-obtusenyne
SYF Mak, NR Curtis, AN Payne, MS Congreve, AJ Wildsmith, CL Francis, JE Davies, SI Pascu, JW Burton, AB Holmes
Chemistry A European Journal | WILEY-V C H VERLAG GMBH | Published : 2008
Abstract
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-metalcatalyzed 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 mediumring oxygen heterocycles are highlighted. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.