66085-04-9Relevant academic research and scientific papers
Catalytic epoxidation of cyclic vinylsilanes by ruthenium(II) complexes under aerobic conditions
Srikanth, Abirami,Nagendrappa, Gopalpur,Chandrasekaran, Srinivasan
, p. 7761 - 7765 (2003)
A new methodology has been developed for the catalytic epoxidation of cyclic vinylsilanes using a ruthenium(II) bisoxazoline complex 2 with molecular oxygen. An attempt has been made to understand the role of -SiMe3 group on the rate of epoxidation process.
Silicon-Controlled Oxidation of Enol Acetates to Enones by Electrochemical Method
Lin, Lung Ching,Chueh, Lu Lin,Tsay, Shwu-Chen,Hwu, Jih Ru
, p. 4093 - 4096 (1995)
Anodic oxidation of β-silylcycloalkanone enol acetates 1a-d in glacial acetic acid containing tetraethylammonium p-toluenesulfonate afforded α,β-unsaturated β-silylcycloalkanones 2a-d exclusively in 81-85percent yields.The silyl group in 1a-d directed the
Silicon-induced ene-type reaction in the thermal conversion of enolates to ss-silyl enones with molecular dioxygen
Hwu, Jih Ru,Chen, Chien Hsien,Hsu, Chuan-I.,Das, Asish R.,Li, Yen Cheng,Lin, Lung Ching
supporting information; experimental part, p. 1913 - 1916 (2009/04/18)
Reaction of alkyl, acetoxy, and silyl enol ethers of 3-(organosilyl) cyclohexanone with molecular dioxygen in toluene at 110 °C produced the corresponding conjugated enones in yields up to 88% yield. The reaction of the same type failed on replacement of
The β-effect of silicon in the orthogonal geometry
Lambert, Joseph B.,Liu, Xiaoyang
, p. 203 - 210 (2007/10/03)
The inductive contribution to the β-effect of silicon has been investigated through the preparation of 1-(trimethylsilyl)bicyclo[2.2.2]octan-2-ol (5-OH) and its sulfonate derivatives. The dihedral relationship in 5 between the trimethylsilyl group and the
Epoxidation versus Allylic Oxidation (CH Insertion) in the Oxyfunctionalization of Vinylsilanes and β-Hydroxy Derivatives by Dimethyldioxirane
Adam, Waldemar,Prechtl, Frank,Richter, Markus J.,Smerz, Alexander K.
, p. 4991 - 4994 (2007/10/02)
Epoxidation of acyclic vinylsilanes by dimethyldioxirane affords α,β-epoxysilanes in high yields, whereas for cyclic vinylsilanes appreciable amounts of allylic oxidation is observed.These competitive pathways become more pronounced, when the reactivity of the double bond is decreased by electronic and/or steric factors.
Enecarboxylation with Diethyl Oxomalonate as an Enophilic Equivalent of Carbon Dioxide. A Synthesis of Allylcarboxylic Acids
Salomon, Mary F.,Pardo, Simon N.,Salomon, Robert G.
, p. 3797 - 3802 (2007/10/02)
Allylcarboxylic acids are prepared from alkenes by a two-stage process which is synthetically equivalent to an ene reaction of carbon dioxide: (1) ene reaction with diethyl oxomalonate to afford an α-hydroxylmalonic ester and (2) oxidative bisdecarboxylation of the derived α-hydroxymalonic acid.The oxidative bisdecarboxylation of α-hydroxymalonic acids can sometimes be achieved with sodium periodate.However, occasionally decarboxylation is only partial, leading to pyruvic rather than carboxylic acids.While the bisdecarboxylations with periodate have previously been "buffered with a little pyridine", the latter is now shown to inhibit the reaction.In fact the pyruvate:carboxylate ratio can be a sensitive function of the amount of pyridine present in the reaction mixture, and the oxidative decarboxylation can be controlled to yield almost exclusively carboxylic or pyruvic acid.An effective new reagent, ceric ammonium nitrate in aqueous acetonitrile, was discovered for oxidative bisdecarboxylation of α-hydroxymalonic acids.Fortunately this reagent provides good to excellent yields of allylcarboxylic acids in many cases for which sodium periodate proved unsatisfactory.
Use of Protected β-Bromocyclopentenones and β-Bromocyclohexenones as β-Acylvinyl Anion Equivalents
Shih, Chuan,Swenton, John S.
, p. 2825 - 2832 (2007/10/02)
Ethylene glycol ketals of the 3-bromocyclohex-2-en-1-one as well as its 2-methyl, 2-n-propyl, and 5,5-dimethyl derivatives have been prepared, and their reactions with butyllithium were studied.The organolithium reagents derived from the above compounds react with a variety of electrophiles to afford after acid hydrolysis the corresponding 3-substituted cyclohexenones.Attempts to prepare the ethylene glycol ketal of 2-methyl-3-bromocyclopent-2-en-1-one gave a low yield of the bromoketal.However, dithioketals of 3-bromocyclopent-2-en-1-one and its 2-methyl derivativecould be prepared in good yield.The metalation chemistry of the dithioketals in both the five- and six-membered-ring series was examined.The functionalization chemistry of the resulting organolithium compounds afforded after dithioketal hydrolysis 3-functionalized cyclohex-2-en-1-ones and cyclopent-2-en-1-ones.Several limitations of the chemistry using allyl bromide and cyclohexenone as electrophiles are noted.
An Efficient and Simple β-Acylvinyl Anion Equivalent for Cyclohexenones
Shih, Chuan,Swenton, John S.
, p. 4217 - 4220 (2007/10/02)
Dilithio species available from treatment of Δ3,4-3-bromocyclohexenone ketals with two equivalents of n-butyllithium serve as one-pot equivalents of β-vinyl-carbanions of cyclohexenones.These former ketals are available in good yield from the corresponding β-bromocyclohexenone by direct ketalization under controlled conditions.
