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.
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).
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 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.
