title: Asymmetric total synthesis of halicholactone.
abstract: The asymmetric total synthesis of the marine metabolite, halicholactone 1, is described. The bisallylic triol 6 with three chiral centers at C8, C12, and C15 was constructed by [2,3]-sigmatropic rearrangement of the sulfoxide 18, which was prepared stereoselectively using the chirality of (diene)Fe(CO)3 complexes. Introduction of the trans-substituted cyclopropane subunit into 21 was successfully achieved using the modified regio- and stereoselective Simmons-Smith reaction. The use of RCM (ring-closing metathesis) methodology (4-->35) was pivotal for the formation of a nine-membered unsaturated lactone fragment of halicholactone 1. As this approach is flexible and stereoselective, other oxylipins could be synthesized by the protocol described herein.
authors: Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors: Y
authors: Y
authors: Baba
authors: G
authors: G
authors: Saha
authors: S
authors: S
authors: Nakao
authors: C
authors: C
authors: Iwata
authors: T
authors: T
authors: Tanaka
authors: T
authors: T
authors: Ibuka
authors: H
authors: H
authors: Ohishi
authors: Y
authors: Y
authors: Takemoto
mesh_terms: D000818:Animals; D007202:Indicators and Reagents; D007783:Lactones / Q000138:chemical synthesis*; D016859:Lipoxygenase Inhibitors / Q000138:chemical synthesis*; D011161:Porifera / Q000737:chemistry*
chemical_list: D007202:Indicators and Reagents; D007783:Lactones; D016859:Lipoxygenase Inhibitors; C431666:halicholactone