- The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
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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.
- Buswell, Marina,Fleming, Ian,Ghosh, Usha,Mack, Stephen,Russell, Matthew,Clark, Barry P.
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p. 3006 - 3017
(2007/10/03)
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- 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
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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.
- Fleming, Ian,Mack, Stephen R.,Clark, Barry P.
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p. 715 - 716
(2007/10/03)
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- A convenient synthesis of hindered amines and α-trifluoromethylamines from ketones
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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.
- Barney, Charlotte L.,Huber, Edward V.,McCarthy, James R.
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p. 5547 - 5550
(2007/10/02)
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