Mukaiyama Aldol Reaction of 1,2-Bis(trimethylsiloxy) Cyclobutene Catalyzed by Magnesium(II) Iodide

Theuniquereactivityof1,2-bis(trimethylsiloxy)cyclobutene(BTCB)towardscarbonylsubstrateoritsacetalequivalentunderLewisacidcatalysiswasfirstrecognizedbyKuwajimaandNakamurain19771.Thereactiongenerallyledtothegeminalacylationorreductivesuccinoylationofcarbonylsubstrateviatheacid-catalyzedpinacol-typerearrangement(acylmigration)oftheMukaiyamaaldoladductasillustratedinEq.12.OR1R2R1R2OROROR1R2OOR=TMSCO2HOR1R2L.A.acidor(1)OTMSOTMS+Furtherdevelopmentofthisreactionhasbeencarriedoutexten…     

First domino mukaiyama-aldol cyclizations of 1, 3-Bis(trimethylsiloxy)-1,3-butadienes with 1,2-diketones

The first domino Mukaiyama-aldol cyclization of 1, 3-bis(trimethylsiloxy)-1,3-dienes with enolizable 1,2-diketones provides a convenient and regioselective access to substituted cyclopent-2-en-1-ones.     

Reaction of bis(trimethylsiloxy)phosphine with trimethylsilane

Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl)propyl]phosphonic acid, respectively, by the reaction with methanol.     

Reaction of Bis(trimethylsiloxy)phosphine with Methyl(phenyl)divinylsilane

Russian Journal of General Chemistry -     

Reaction of 1, 1-Bis(Methylthio)-3-Methyl-1, 3-Butadiene with Lithiated 3-Methyl-2-Butenyl Phenyl Sulfide. A Special Case of Cyclopropane Formation

Abstract

The conjugated ketene dithioacetal 2 is now available by three different procedures¹. This electrophilic isoprene compound has been shown to add smoothly some simple lithio derivatives, but the addition of 3-methyl-2-butenyl-lithium gave a product with total inversion of the starting allylic chain^1a.     

Reaction of 2,3-Bis(benzotriazol-1-yl)-1,4-naphthoquinone

Russian Journal of General Chemistry -     

Reaction of α,α′ - bis(trimethylsiloxy) sulfides with low valent titanium reagents

We have shown that low valent titanium reagents reductively couple α,α′ -bis-(trimethylsiloxy) sulfidees giving olefins in good yield. With unsymmetrical $\text{1}$, mixed olefins are obtained suggesting an intermolecular pathway. Finally, we have demonstrated that $\text{trans}$-episulfide $\text{3}$ is quantitatively converted to $\text{trans}$-stilbene.     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六羰基钼的反应

１,２－双（四甲基环戊二在）四甲基二硅烷与正丁基锂作用生成（四甲基二硅撑）双（四甲基环戊二烯基负离子盐）,后者随即与六羰基钼反应形成１,１＇－（四甲基二硅撑）双（四甲基环戊二烯基钼负离子盐）－－（Ｍｅ２ＳｉＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３－Ｌｉ＾＋〗２（１）,１与冰醋酸作用,随即分别与ＣＣＩ４,ＮＢＳ及Ｉ２反应,生成相应的钼卤化合物（Ｍｅ２ＳＩＳｉＭｅ２）〖Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｘ〗２〖Ｘ     

An unusual reaction of 1,1-dilithio-2,3,4,5-tetraphenyl-1-silacyclopentadiene with diphenylcyclopropenone: synthesis of 1,4-Bis(trimethylsiloxy)-2,3,5,6-tetraphenylbenzene

Reaction of 1,1-dilithio-2,3,4,5-tetraphenylsilole (*5*) with diphenylcyclopropeneone proceeds with loss of silicon to yield the dilithium salt of 2,3,4,5-tetraphenyl-1,4-hysroquinone (*8*), which was trapped with trimethylchlorosilane to yield 1,4-bis(trimethylsiloxy)-2,3,5,6-tetraphenylbenzene, *9*. A possible pathway for the formation of *8* and *9* is proposed.     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me₂SiSiMe₂)[Me₄CpMo(CO)₃-Li⁺]₂(I),I与冰醋酸作用,随即分别与CCl₄,NBS及I₂反应,生成相应的铝卤化合物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃X]₂[X=Cl(1),Br(2),I(3)].I与CH₃I反应,在钼原子上发生烃基化,得到产物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃Me]₂(4);I与单质I₂直接反应,生成脱硅桥产物Me₄Cp(CO)>₃I(5).经元素分析、IR及¹HNMR表征了化合物1-5的结构。     

Reaction of 1-Methylindole with Dimethyl-Acetylenedicarboxylate an 2:1 Adduct-Dimethyl α, α-Bis(1-Methylindol-3-YL)-Succinate

The structure of 2:1 adduct of 1-methylindole and dimethyl acetylenedicar-boxylate was elucidated as dimethyl α, α-bis(1-methylindol-3-yl)-succinate. Some of its derivatives were prepared.     

Unusual Desilanolysis of 1,1-Dimethyl-1-(trimethylsiloxy)-3-phenylpropyne

Russian Journal of General Chemistry -     

Three-Component Reaction of 1H-Pyrrole-2,3-diones with Tetronic Acid. Synthesis of 4,4-Bis(furan-3-yl)pyrroles

Russian Journal of Organic Chemistry - Ethyl 1-aryl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrole-3-carboxylates reacted with tetronic acid in boiling anhydrous toluene in the presence of acetic acid...     

Reaction of 1,5-Bis(polyfluoroalkyl)-1,3,5-triketones with Amidines

Russian Journal of Organic Chemistry - Previously unknown 4-(polyfluoroacylmethyl)-substituted pyrimidines were synthesized by reaction of 1,5-bis(polyfluoroalkyl)-1,3,5-triketones with amidines.