The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
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.
p. 3006 - 3017
(2007/10/03)
1,1-Disilyl alcohols as d1 synthons: Harnessing the 1,2-Brook rearrangement
1,1-Disilyl alcohols like 6 give the silyl ethers like 9 on treatment with base and alkyl halides, in a reaction which may be formulated as the alkylation of the Brook-rearranged carbanion 8. The products can be oxidised to give ketones like 10, showing that this Brook-rearranging system supplies a controlled d1 synthon of the acyl anion class. The alcohols can be prepared from the acid chloride 12 and dimethyl(phenyl)silyllithium, but the intermediate anion 21 need not be worked up; it can be used directly in the alkylation step.
Fleming, Ian,Lawrence, Annabel J.,Richardson, Robert D.,Surry, David S.,West, Mark C.
p. 3349 - 3365
(2007/10/03)
Synthesis of Acylsilanes from Amides and Esters, and the Selective Oxidation of α-Silyl Alcohols to Aldehydes
The acylsilanes 2 can easily be made directly from the dimethylamides 3 by treatment with phenyldimethylsilyllithium.They can also be made in two steps from the esters 4 using 2 equiv. of phenyldimethylsilyllithium followed by oxidation of the disilyl alcohols 5 with PDC.The disilyl alcohols 5 can be used as intermediates in the conversion of esters into aldehydes without recourse to hydride reagents, by monodesilylation, using a Brook rearrangement, followed by oxidation and selective removal of the silyl group, using chromium trioxide in DMSO.
Fleming, Ian,Ghosh, Usha
p. 257 - 262
(2007/10/02)
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