70160-87-1Relevant academic research and scientific papers
The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
Buswell, Marina,Fleming, Ian,Ghosh, Usha,Mack, Stephen,Russell, Matthew,Clark, Barry P.
, p. 3006 - 3017 (2007/10/03)
The reactions of the silyllithium reagent with tertiary amides was discussed. The enediamines were easily isomerized from cis to trans, easily oxidized to dienediamines and were hydrolyzed to α-aminoketones. If the two equivalents of the silyllithium reagent were used, the product was an α-silylamine. The results show that each member of the homologous series of amides gives rise to a substantially different product.
Formation of α-dialkylamino alkyllithium intermediates in the reaction of N,N-dialkylamides with PhMe2SiLi followed by a second lithium reagent, and their alkylation, fragmentation, cyclisation and rearrangement by proton transfer
Fleming, Ian,Mack, Stephen R.,Clark, Barry P.
, p. 715 - 716 (2007/10/03)
Tertiary amides (RCONMe2) react with PhMe2SiLi, followed by a second lithium reagent NuLi, to give α-dialkylamino alkyllithium intermediates R(Me2N)CLiNu that undergo protonation 2 → 3, alkylation 2a → 3ab, β-elimination 5 → 6, intramolecular attack on an isolated double bond 9 → 10, intramolecular proton transfer 12, 17 and 22 (arrows), and fragmentation 28 and 34 (arrows), depending upon the structures of the various components R and Nu.
A convenient synthesis of hindered amines and α-trifluoromethylamines from ketones
Barney, Charlotte L.,Huber, Edward V.,McCarthy, James R.
, p. 5547 - 5550 (2007/10/02)
Ketones and α-trifluoromethylketones were converted to primary, secondary, and tertiary amines in good to excellent yields by a reductive amination procedure utilizing TiCl4/NaCNBH3. The method provides the first direct route to α-trifluoromethylamines from ketones, and access to hindered amines from ketones which are unobtainable by Borch reductive amination.
