77815-44-2Relevant academic research and scientific papers
Influence of the silyl group on the reactivity of some ortho-lithiated aryl alkyl sulfides
Durka, Krzysztof,Klis, Tomasz,Serwatowski, Janusz,Wozniak, Krzysztof
, p. 3145 - 3148 (2013/07/19)
The lithiation of brominated aryl (α-dimethylsilyl)alkyl sulfides in diethyl ether produces stable heterocyclic silanes, which were characterized by 1H, 13C, and 29Si NMR spectroscopy and by X-ray crystallography. The reaction involves the intramolecular attack of the phenyl carbanion on the silicon atom with the formation of a pentacoordinated silicon intermediate. The stability of the formed intermediate depends on the solvent. It decomposes easily in THF at -78 C with Si-C bond cleavage; however, it is stable in diethyl ether at room temperature. Addition of water results in the Si-H bond cleavage, while the heterocyclic ring containing the silicon atom is conserved.
Synthesis of Alkenes via Peterson Reaction
Ager, David J.
, p. 183 - 194 (2007/10/02)
The α-phenylthiosilanes (2) have been used to prepare the α-silyl anions (1) by reaction with lithium naphthalenide; subsequent condensation with a carbonyl compound gave the alkene (8) via the Peterson reaction.The α-phenylthiosilanes (2) were prepared from n,n-bis(phenylthio)acetals (4) by reaction with lithium naphthalenide and chlorotrimethylsilane.The n,n-bis(phenylthio)acetals (4) were obtained, in turn, from 1,1-bis(phenylthio)acetals (5) by anion formation with butyl-lithium-N,N,N',N'-tetramethylethylenediamine complex in hexane followed by reaction with an alkyl halide.The Peterson reaction was also used to prepare vinyl sulphides (9) and vinyl sulphones (13).
The Synthesis of Ketones via α-Silyl Sulphides
Ager, David J.
, p. 195 - 204 (2007/10/02)
α-Phenylthiosilanes (2) have been prepared by alkylation of the anion (4) derived from the 1-phenylthio-1-trimethylsilylalkane (1).These anions (4) have benn prepared by a variety of methods including, direct deprotonation of (1), displacement of a phenylthio group by lithium naphthalenide addition of an alkyl-lithium to 1-phenylthio-1-trimethylsilylethene (7), and transmetallation of a tributylstannyl moiety.The formation of an alkyl-lithium by reaction of lithium naphthalenide with a phenyl sulphide provided an additional route to (2) from bis(phenylthio)acetals (8).An alternative path to the α-phenylthiosilanes (2) was to reduce the corresponding α-phenylsulphonylsilane (15); these, in turn, being readily available from alkylation or silylation of α-sulphonyl anions.The α-phenylthiosilanes (2) were converted into the O-trimethylsilylphenylthioacetal (18) by the sila-Pummerer rearrangement, although this was complicated by vinyl sulphide (20) formation in certain cases.Subsequent hydrolysis of (18) and (20) gave the ketone (3).
THE PREPARATION OF PHENYL KETONES USING (PHENYLTHIO)PHENYL(TRIMETHYLSILYL)METHYL-LITHIUM
Ager, David J.
, p. 4759 - 4762 (2007/10/02)
Phenyl ketones are prepared by alkylation of (phenylthio)phenyl(trimethylsilyl)methyl-lithium followed by oxidation and rearrangement.
