A simple synthesis of nitriles from aldoximes.
Easily synthesized aldoximes have been converted to the corresponding nitriles under very mild conditions by a simple reaction with 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP) and DBU in CH(2)Cl(2), THF, or DMF. As an alternative reagent that eliminates the formation of hexamethylphosphoramide as a byproduct, use of 1H-benzotriazol-1-yl-4-methylbenzenesulfonate (Bt-OTs) and DBU was investigated. Reactions with this reagent also proceeded smoothly and in good yields, although in one case N-sulfonylation was observed. An attempt to gain mechanistic insight into the BOP-mediated reaction has been made using (31)P{(1)H} NMR. However, no phosphorus-bearing intermediate could be readily observed. Finally, the method has been applied to the synthesis of an antiviral 4'-cyano adenosine analogue from a commercial precursor using a single saccharide protecting group.
Singh
Manish K
MK
Department of Chemistry, The City College and The City University of New York, 160 Convent Avenue, New York, New York 10031-9198, USA.
Lakshman
Mahesh K
MK
D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009005:Monosaccharides / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis*; D009943:Organophosphorus Compounds / Q000737:chemistry; D010091:Oximes / Q000737:chemistry*
D009005:Monosaccharides; D009570:Nitriles; D009943:Organophosphorus Compounds; D010091:Oximes