ortho-Metalation of enantiopure aromatic sulfoxides and stereocontrolled addition to imines.
Enantiopure aromatic (phenyl, naphthyl) and heteroaromatic (pyridyl, quinolyl, diazinyl) sulfoxides have been synthesized by reaction of (S)-tert-butyl tert-butanethiosulfinate with aryl- or heteroaryllithium derivatives. The ortho-directed metalation of the sulfoxides was performed with lithium bases. Subsequent addition of the lithiated intermediates to N-tosylimines afforded tosylaminoalkyl tert-butylsulfinyl arenes. In most cases a complete asymmetric induction was highlighted in favor of (S,S) isomers. Heating the aminosulfoxides provided an original cyclization to form novel cyclic sulfenamides. A novel enantiopure synthesis of a benzylamine was described. An application of an enantiopure aminosulfoxide as N,S ligand for the asymmetric catalysis of allylic nucleophilic substitution has been successfully tested.
Laboratoire de Chimie Organique Fine et Hétérocyclique, UMR CNRS 6014, IRCOF, INSA, B.P. 08, 76131 Mont Saint Aignan, France.
Nicolas
N
Le Fur
Ljubica
L
Mojovic
Nelly
N
Plé
Alain
A
Turck
Vincent
V
Reboul
Patrick
P
Metzner
D001596:Benzylamines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D008670:Metals / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013454:Sulfoxides / Q000138:chemical synthesis* / Q000737:chemistry
D001596:Benzylamines; D006841:Hydrocarbons, Aromatic; D007097:Imines; D008024:Ligands; D008670:Metals; D009942:Organometallic Compounds; D013454:Sulfoxides