title: Revision of absolute configuration of enantiomeric (methylenecyclopropyl)carbinols obtained from (R)-(-)- and (S)-(+)-epichlorohydrin and methylenetriphenylphosphorane. Implications for reaction mechanism and improved synthesis of antiviral methylenecyclopropane analogues of nucleosides.
abstract: Absolute configurations of enantiomeric methylenecyclopropanecarbinols obtained by reaction of (R)- and (S)-epichlorohydrin 5 with methylenetriphenylphosphorane or resolution of the corresponding oxaphospholane 6 via a salt with L-(+)-tartaric acid and subsequent Wittig transformation with formaldehyde were revised. The (-)-oxaphospholane 6 has the S,S and (-)-(methylenecyclopropyl)carbinol (4) the R configuration. The configurations of (+)-6 and (+)-4 are then R,R and S, respectively. These assignments are in accord with an initial attack of phosphorane at the oxirane ring of epichlorohydrin. An improved preparation of key enantiomeric intermediates (R)-1a and (S)-1a, important for synthesis of antiviral purine methylenecyclopropane analogues of nucleosides, is also described.
authors.affiliation: Department of Chemistry, Developmental Therapeutics Program, Barbara Ann Karmanos Cancer Institute, Wayne State University School of Medicine, Detroit, Michigan 48201-1379, USA.
authors.forename: Xinchao
authors.initials: X
authors.lastname: Chen
authors.forename: Jiri
authors.initials: J
authors.lastname: Zemlicka
mesh_terms: D000225:Adenine / Q000031:analogs & derivatives*; D000998:Antiviral Agents / Q000138:chemical synthesis* / Q000737:chemistry; D003521:Cyclopropanes / Q000737:chemistry*; D004811:Epichlorohydrin / Q000737:chemistry; D000432:Methanol / Q000031:analogs & derivatives* / Q000737:chemistry*; D015394:Molecular Structure; D009705:Nucleosides / Q000737:chemistry; D010753:Phosphoranes / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000998:Antiviral Agents; D003521:Cyclopropanes; D009705:Nucleosides; D010753:Phosphoranes; D004811:Epichlorohydrin; D000225:Adenine; D000432:Methanol