title: Total synthesis of antheliolide A.
abstract: The first synthesis of the structurally unique marine natural product antheliolide A (1) has been accomplished by the pathway outlined in Scheme 1. The sequence is stereocontrolled and has led to the synthesis of (+/-)-1, and ent-1 as well as 1. The route contains a number of noteworthy or novel steps including (1) formation of the mixed acetal 7, (2) the diastereoselective bicyclization to form 8 in which stereocenters are correctly established at each carbon of the four-membered ring, (3) the chain extension 8 --> 11, (4) the efficient closure of the nine-membered ring of 12, (5) the mild oxidative cleavage sequence 14 --> 17, and (6) the successful and quick formation of the last three rings of 1 from aldehyde 17 via 18. The synthesis of 1 has also resulted in the clarification of its absolute configuration, which had not been determined previously.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
authors.forename: Chandra Sekhar
authors.initials: CS
authors.lastname: Mushti
authors.forename: Jae-Hun
authors.initials: JH
authors.lastname: Kim
authors.forename: E J
authors.initials: EJ
authors.lastname: Corey
mesh_terms: D002851:Chromatography, High Pressure Liquid; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry / Q000302:isolation & purification; D009682:Magnetic Resonance Spectroscopy; D013237:Stereoisomerism
chemical_list: D006571:Heterocyclic Compounds; D006576:Heterocyclic Compounds, 4 or More Rings; C522715:antheliolide A