title: General Stereodivergent Enantioselective Total Synthetic Approach toward Macrosphelides A-G and M.
abstract: A straightforward enantioselective total synthesis algorithm for the preparation of 8 out of 13 macrosphelides within 9-11 steps starting from tert-butyl sorbate is presented. The use of a cyclic sulfate as both protecting and reactivity directing group is the key element within this algorithm. A high-pressure transesterification allows for the selective ring-enlargement of the 15-membered macrosphelides into the 16-membered counterparts. The absolute configurations of the natural products were unambiguously assigned both by the chemical synthesis and by X-ray structure analysis.
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, DE-70569 Stuttgart, Germany.
authors.forename: Christine
authors.initials: C
authors.lastname: Häcker
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, DE-70569 Stuttgart, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Plietker
mesh_terms: D000465:Algorithms; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D006571:Heterocyclic Compounds; D007783:Lactones; C000603240:macrosphelide G; C000603241:macrosphelide M