title: Stereoselective Peterson olefinations from bench-stable reagents and N-phenyl imines.
abstract: The synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N-benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N-bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained.
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland).
authors.forename: Manas
authors.initials: M
authors.lastname: Das
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland).
authors.forename: Atul
authors.initials: A
authors.lastname: Manvar
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland).
authors.forename: Maïwenn
authors.initials: M
authors.lastname: Jacolot
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland).
authors.forename: Marco
authors.initials: M
authors.lastname: Blangetti
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland).
authors.forename: Roderick C
authors.initials: RC
authors.lastname: Jones
authors.affiliation: Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephen's Green, Dublin 2 (Ireland). donalfoshea@rcsi.ie.
authors.forename: Donal F
authors.initials: DF
authors.lastname: O'Shea
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis; D007097:Imines / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D007097:Imines
keywords: Peterson olefination; bench-stable reagents; imines; organic synthesis; stereoselectivity