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.
Le Fur
Nicolas
N
Laboratoire de Chimie Organique Fine et Hétérocyclique, UMR CNRS 6014, IRCOF, INSA, B.P. 08, 76131 Mont Saint Aignan, France.
Mojovic
Ljubica
L
Plé
Nelly
N
Turck
Alain
A
Reboul
Vincent
V
Metzner
Patrick
P
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