Total synthesis of solandelactones E and F, homoeicosanoids from the hydroid Solanderia secunda.
Asymmetric total syntheses of solandelactones E and F confirmed that hydroxyl configuration at C11 in these oxylipins had been misassigned and that the stereochemistry at this center should be reversed. Key steps in the synthesis involved a Nagao asymmetric acetate aldol reaction, a directed Simmons-Smith cyclopropanation, a Holmes-Claisen rearrangement to establish the unsaturated octalactone, and a Nozaki-Hiyama-Kishi coupling to connect two major fragments at C11-C12.
White
James D
JD
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA. james.white@oregonstate.edu
Martin
William H C
WH
Lincoln
Christopher
C
Yang
Jongtae
J
D000085:Acetates / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D003521:Cyclopropanes / Q000737:chemistry; D015777:Eicosanoids / Q000138:chemical synthesis* / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D008386:Marine Biology; D015394:Molecular Structure; D013237:Stereoisomerism
D000085:Acetates; D000447:Aldehydes; D003521:Cyclopropanes; D015777:Eicosanoids; D007783:Lactones; C519028:solandelactone E; C523382:solandelactone F; C116609:3-hydroxybutanal; C030797:cyclopropane