title: Spirodiepoxides: synthesis of epoxomicinoids.
abstract: Three closely related analogues of epoxomicin have been synthesized. Allene-derived spirodiepoxides were key intermediates. Spirodiepoxide formation and stereochemical dependence on solvent, oxidant, and allene structure were cataloged. The facial selectivity of the first epoxidation of 1,3-disubstituted and trisubstituted allenes was found to be >20:1 with dimethyldioxirane in chloroform. For stereogenic allenes, the facial selectivity of the second oxidation is dependent primarily on allene structure and secondarily on solvent and oxidant. For the acyclic systems evaluated this ratio was as high as 8:1. A conformational model is advanced to account for these observations.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA.
authors.forename: Yue
authors.initials: Y
authors.lastname: Zhang
authors.forename: Joseph R
authors.initials: JR
authors.lastname: Cusick
authors.forename: Partha
authors.initials: P
authors.lastname: Ghosh
authors.forename: Ning
authors.initials: N
authors.lastname: Shangguan
authors.forename: Sreenivas
authors.initials: S
authors.lastname: Katukojvala
authors.forename: Jennifer
authors.initials: J
authors.lastname: Inghrim
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Emge
authors.forename: Lawrence J
authors.initials: LJ
authors.lastname: Williams
mesh_terms: D008956:Models, Chemical; D015394:Molecular Structure; D009842:Oligopeptides / Q000138:chemical synthesis / Q000737:chemistry; D013141:Spiro Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009842:Oligopeptides; D013141:Spiro Compounds; C078846:epoxomicin