The geometry of displacements at nonstereogenic atoms: the formal displacement of alkoxide from alkoxyamines by organolithium reagents

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

“…[134][135][136][137][138][139][140][141][142][143] Genêt and co-workers aminated aryl, primary and secondary alkyllithiums using lithium tbutyl-N-tosyloxycarbamate (LiBTOC), 21a, to synthesize primary amines in their N-Boc protected form (Scheme 45). 116,117,119 LiBTOC 21a reacts with organolithium reagents according to the mechanism proposed by Beak and coworkers.…”

Recent methodologies toward the synthesis of valdecoxib: A potential 3,4-diarylisoxazolyl COX-II inhibitor

“…50 When 30 is unsubstituted or substituted with a methyl group (R= H, Me), 2-alkyn-1-one O -methyl oxime tend to isomerize to 31 when passed through silica gel and often resulted in a mixture of E/Z isomers in 1:1 ratio. However, with increase of the size of the R group, the Z isomer was predominantly the major isolated product (Scheme 9).…”

“…50 Additional Heck 51 and Sonogashira 52 coupling reactions of 4-iodo-5-methyl-3-phenylisoxazole 46 with phenyl acetylene 50 and N -acryloylmorpholine 51 provided the desired 4-acetlyated isoxazole 52 and α,β-unsaturated amide 53 in high yields (Scheme 14). …”

Competitive kinetic study of the amination of organomagnesium and -zinc reagents with acetoneO-sulfonyloxime

“…Beak's group, in a series of detailed papers, reported on the mechanistic investigation of amination of organolithiums 14,15 and α-lithionitriles 16 with O-methylhydroxylamine (1a) 14,15 and O-(diarylphosphinyl) hydroxylamine (1c) 16 and provided evidence for a polar S N 2-like mechanism. Ricci and coworkers, in their work on the amination of higher order lithium cuprates with 1e, offered a mechanism 17 that closely follows Beak's approach.…”