Regiospecificity and conformational specificity in oxime alkylation of a geometrical enantiomeric isomer

Abstract

64872-41-9; 1 [X = C(CH3)2Cl], 64872-42-0; 2 (X = CH3), 64872-43-1; 2 (X = CzHs), 64872-44-2; 2 (X = CI), 64872-45-3; 3 (X = CH3), 23062-66-0; 3 (X = C2H5). 23062-67-1; 3 [X = CH(CH3)2], 23102-73-0; 3 [X = C(CH3)3] 64872-46-4; 3 (X = Cl), 33732-68-2; 3 (X = COCHB), 64872-47-5; 3 [X = C(CH3)20H], 64872-48-6; 3 [X = C(CH3)&1], 64872-49-7; trimethylaluminum, 75-24-1; triethylaluminum, 97-93-8; tributyltin hydride, 688-73-3.

Nucleophilic Addition to Imines and Imine Derivatives

“…Ketone dimethylhydrazones generally deprotonate on the less-substituted a-carbon, regardless of the C N geometry.6 Alkyllithium-mediated deprotonation of ketimines, however, generally occurs anti to the nitrogen substituent.? For example, BusLi (THF) treatment of 2-methylcyclohexanone-derived N,N-dimethylhydrazone (3) and N-cyclohexylimine (4) followed by the addition of benzyl chloride results in syn (100:0) and anti (87:13) a-alkylation, respectively. …”

“…>=N' H >=N' SiMe 3 >=N' SR (203) (204) (205) Demonstration that N-trimethylsilylimines (which are sometimes too unstable to isolate) can be generated and treated in situ with organometallic reagents has increased the scope and utility of these reactions for the preparation of substituted primary amines. l44 Nonenolizable aldehydes, for instance, condense with lithium bis(trimethylsilyl)amide to afford solutions of N-trimethylsilylaldimines.…”