150614-88-3Relevant academic research and scientific papers
Efficient synthesis of acylsilanes using morpholine amides
Clark, Christopher T.,Milgram, Benjamin C.,Scheidt, Karl A.
, p. 3977 - 3980 (2004)
(Chemical Equation Presented) A general synthesis of acylsilanes from the corresponding morpholine amides and silyllithium species is described. The use of morpholine amides is economical and prevents over-addition by the silyl nucleophile. The procedure cleanly affords acylsilanes in good yields and circumvents the use of stoichiometric copper(I) cyanide typically employed to synthesize these compounds from acid chlorides.
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.
Newly designed acylsilanes as versatile tools in organic synthesis
Bonini, Bianca F.,Comes-Franchini, Mauro,Fochi, Mariafrancesca,Mazzanti, Germana,Ricci, Alfredo
, p. 181 - 189 (2007/10/03)
Structural variations in acylsilane molecules allow a number of new selective synthetic processes to be performed which lead to sulfur-containing heterocycles, highly functionalized and unsaturated polycarbonyl derivatives, polyenes, and β- and γ-aminoalcohols. The synthesis of these compounds, most of them not easily accessible through conventional routes, takes advantage of the site-selective reactions occurring at the C-Si bonds, of the increased stability of acylsilanes with respect to that of the corresponding aldehydes and of the high diastereofacial selectivity introduced by the SiR3 group. Herein we report the different synthetic strategies leading to the synthesis of several functionalized acylsilanes and their synthetic applications. The use of new selective polymetallic reagents for the nucleophilic silylation will be presented as well.
Synthesis of functionalized acylsilanes from carboxylic acid chlorides and silyl-zinc cyanocuprates
Bonini,Comes-Franchini,Mazzanti,Passamonti,Ricci,Zani
, p. 92 - 96 (2007/10/02)
The high yielding synthesis of a variety of acylsilanes, most of them unknown and bearing reactive functionalities, has been accomplished by reaction between carboxylic acid chlorides and a novel silyl-zinc cyanocuprate acting as a silyl anion source. The advantages offered by this procedure with respect to those previously reported, based on carboxylic acid chlorides or on different starting materials, as well as with respect to the use of standard silyl cyanocuprates, are discussed herein.
Chemistry of Silyl Thioketones. Part 7. Synthesis, Cycloaddition and Oxidation of Cycloalkyl Silyl Thioketones and Desilylation of the Reaction Products
Bonini, Bianca F.,Busi, Filippo,Laet, Roland C. de,Mazzanti, Germana,Thuring, Jan-Willem J. F.,et al.
, p. 1011 - 1018 (2007/10/02)
Cycloalkyl silyl thioketones 3, achiral as well as chiral at carbon, have been synthesized by thionation of the corresponding acyl silanes 2.During thionation of 2a, 2d and 2f unexpected products were observed.Cycloaddition reactions of cycloalkyl silyl thioketones 3 with buta-1,3-diene have been performed.A diastereoisomeric excess (d.e.) of 80percent was obtained in the case of chiral thione 3e.Desilylation of the cycloadducts was only possible at the stage of the corresponding α-silyl sulfones 11.Oxidation of compounds 3 led to the corresponding (E)-silyl sulfines 13 which by stereospecific fluorodesilylation gave (Z)-thioaldehyde S-oxides 14.Compound 14e is the first example of enantiomerically pure mono-substituted sulfine (thioaldehyde S-oxide).
