title: Enantioselective catalytic fluorinative aza-semipinacol rearrangement.
abstract: An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.
authors.affiliation: Department of Organic Chemistry, ‡Laboratory of Crystallography, and §Department of Physical Chemistry, University of Geneva , Quai Ernest Ansermet 30 CH-1211 Geneva 4, Switzerland.
authors.forename: Fedor
authors.initials: F
authors.lastname: Romanov-Michailidis
authors.forename: Marion
authors.initials: M
authors.lastname: Pupier
authors.forename: Céline
authors.initials: C
authors.lastname: Besnard
authors.forename: Thomas
authors.initials: T
authors.lastname: Bürgi
authors.forename: Alexandre
authors.initials: A
authors.lastname: Alexakis
mesh_terms: D000588:Amines / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry; D002384:Catalysis; D053138:Cyclohexenes / Q000737:chemistry*; D003979:Diazonium Compounds / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000588:Amines; D001372:Aza Compounds; D001880:Boranes; D053138:Cyclohexenes; D003979:Diazonium Compounds; D006845:Hydrocarbons, Fluorinated; C533353:selectride; C519041:semipinacol; C408750:selectfluor