Chlorotrimethylsilane: A Powerful Lewis Acidic Catalyst in Michael‐Type Friedel–Crafts Reactions of Indoles and Enones

Catalytic amount of chlorotrimethylsilane (TMSCl) was found to be an effective silicon Lewis acid catalyst in catalyzing the Michael‐type Friedel–Crafts reactions of indoles and chalcones to afford corresponding 3‐substituted indole derivatives in good to excellent yields. The method is metal‐free, has mild reaction conditions, and generates good yields of products with greater selectivity, which make it a useful and attractive process for the synthesis of different indole derivatives.     

微波辐射促进选择性合成4,6-二芳基-3,4-二氢嘧啶-2(1H)-酮和嘧啶-2(1H)-酮

探讨了在微波加热条件下,芳香醛、取代苯乙酮和尿素的三组分反应在N,N-二甲基甲酰胺(DMF)中制得4,6-二芳基-3,4-二氢嘧啶-2(1H)-酮类化合物,收率为68%～84%.若在反应体系中加入三甲基氯硅烷,该三组分反应则高产率(66%～87%)地生成相应的脱氢产物4,6-二芳基嘧啶-2(1H)-酮类化合物.该反应具有反应条件温和、产物收率高、操作方便等优点,为4,6-二芳基-嘧啶-2(1H)-酮类药物中间体的合成提供了一条全新的路线.     

Polymer supported naphthalene-catalysed sodium reactions

Arene-catalysed sodium reactions have been utilised in the generation of organosodium complexes, from a variety of organochloride complexes, in high yield. Phenyltrimethylsilane, benzene and 2-methyl-1-phenyl-1-propanol were prepared in yields >80%, using polymer supported naphthalene-catalysed sodium reactions, whereby phenylsodium, prepared from the reaction of chlorobenzene, sodium powder and polymer-supported naphthalene (5-100%), was quenched with chlorotrimethylsilane, water or Pr(i)CHO respectively.     

Asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones by rhodium-catalyzed 1,4-addition of arylzinc reagents in the presence of chlorotrimethylsilane

[reaction: see text] The first catalytic asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones has been developed by way of a rhodium-catalyzed 1,4-addition of arylzinc reagents to 4-quinolones. These 1,4-adducts can be obtained with high enantioselectivity by the use of (R)-binap as a ligand, and high yields are realized by conducting the reactions in the presence of chlorotrimethylsilane.     

Chlorotrimethylsilane-nitrate salts as oxidants: direct oxidative conversion of thiols and disulfides to sulfonyl chlorides

A mixture of nitrate salt and chlorotrimethylsilane is found to be a mild and efficient reagent for the direct oxidative conversion of thiols (1) and disulfides (2) to the corresponding sulfonyl chlorides (3) in excellent yields through oxidative chlorination. Sulfides and sulfoxides were also found to undergo oxidation to sulfones under similar reaction conditions. In most cases these reactions are highly selective, simple, and clean, affording products in high yield and purity.     

AlCl3催化歧化制备二甲基二氯硅烷的DFT和MP2研究(II)

研究一甲基三氯硅烷与三甲基氯硅烷分别与三氯化铝作用并得到中间体后, 中间体分别与一甲基三氯硅烷和三甲基氯硅烷作用的机理, 反应的IRC (Intrinsic reaction coordinate)曲线, 各关键原子沿IRC的变化曲线及产物的理论产率. 结果发现, 中间体趋于与一甲基三氯硅烷作用生成二甲基二氯硅烷, 且三甲基氯硅烷的转化率高于一甲基三氯硅烷. 实验结果与计算结果吻合.     

Rapid,high-yield cleavage of enol and dienol methyl ethers under mild conditions using chlorotrimethylsilane/sodium iodide

A number of enol and dienol methyl ethers are rapidly cleaved to aldehydes and ketones in quantitative yields by the use of chlorotrimethylsilane/sodium iodide.     

AlCl_3催化歧化制备二甲基二氯硅烷的DFT和MP2研究(II)

研究一甲基三氯硅烷与三甲基氯硅烷分别与三氯化铝作用并得到中间体后,中间体分别与一甲基三氯硅烷和三甲基氯硅烷作用的机理,反应的IRC(Intrinsicreactioncoordinate)曲线,各关键原子沿IRC的变化曲线及产物的理论产率.结果发现,中间体趋于与一甲基三氯硅烷作用生成二甲基二氯硅烷,且三甲基氯硅烷的转化率高于一甲基三氯硅烷.实验结果与计算结果吻合.     

3-Neopentylallyllithium II. Reactions in hydrocarbon media

Product distributions are reported for several reactions in hydrocarbon solvent of 3-neopentylallyllithium, the 1,4-addition product of tert-butyllithium and 1,3-butadiene. Protolysis with several agents yields predominately the “normal” products [(Ia) and (Ib)] with less than 6% of the terminal olefin observed. The ratio of the cis/trans isomers [(Ia) and (Ib)] parallels the ratio of the lithiated forms before protolysis. Reaction with chlorotrimethylsilane also shows no “rearranged” product. Carboxylation and ketone addition reactions, however, proceed with marked rearrangement unless the ketone is very hindered. Di-tert-butyl ketone and benzophenone give no rearranged product. Addition of a second mole of butadiene also results in predominant (60%) rearrangement of the neopentylallyl group. Bromination with molecular bromine and 1,2-dibromoethane yields a mixture of dibromo-derivatives in the former case and C₁₆-diolefin coupling products in the later case. Tentative mechanisms for protolysis and addition reactions are discussed.     

Sodium Bromide Catalysed Regioselective Cleavage of Oxitanes with Chlorotrimethylsilane

Sodium bromide efficiently catalyses the regioselective cleavage of oxiranes with chlorotrimethylsilane to the corresponding O-silylated chlorohydrins in excellent yields.     

稀土金属作用下芳香醛、酮的还原偶联反应

由Ln/ROH/TMSCl组成的体系能选择性地使芳香族醛、酮还原偶联形成频哪醇, 产率优良, 而对脂肪族醛酮呈惰性。     

Allylation of Aldehydes and Ketones with Allyl Bromide and Tin Promoted by Me3SiCI and Alcohol

Allylation of aldehydes and ketones to give homoallylic alcohols can be carried out successfully with allyl bromide and metallic tin under anhydrous condition. The 64–89% yields of homoallyl alcohols are obtained by addition of chlorotrimethylsilane as a promoter in anhydrous methanol.     

无水稀土氯化物的新制备方法: 从稀土氧化物出发制备无水稀土氯化物

本文报道从稀土金属氧化出发, 在THF中与TMSCl/CH3OH反应, 制备无水稀土氯化物LnCl3.nTHF的方法。此法具有产物纯度高, 产率好, 制备条件温和, 操作方便等优点, 因而具有一定的实用性。     

Transformation of Amides into Esters by the Use of Chlorotrimethylsilane

A mild transformation of various amides and imides into the corresponding esters and diesters in good yields by using chlorotrimethylsilane and alcohols at rt are described. Either primary, secondary, or tertiary amide or imide can be used in this transformation. Primary and secondary alcohols gave better yields than tertiary alcohols.     

Zinc metal-promoted nucleophilic addition of nonactivated alkyl iodides to aromatic aldimines in the presence of chlorotrimethylsilane in ethyl acetate-DMI

A variety of aromatic aldimines react with nonactivated alkyl iodides in the presence of zinc powder and a catalytic amount of chlorotrimethylsilane (TMSCl) in ethyl acetate-DMI to afford the corresponding α-alkylbenzylamine derivatives in good to excellent yields.     

Zirconocene Dichloride–Catalyzed Pinacol Coupling of Aromatic Aldehydes and Ketones

The reductive coupling of aromatic aldehydes and ketones has been achieved using a catalytic amount of zirconocene dichloride in the presence of magnesium metal and chlorotrimethylsilane in THF at room temperature to afford the corresponding 1,2‐diols in good yields and diastereoselectivity.     

Reductive coupling of aromatic N,N-acetals using zinc and chlorotrimethylsilane

The reductive coupling of aromatic N,N-acetals and N,O-acetal activated by chlorotrimethylsilane proceeded smoothly in the presence of zinc to give the corresponding diamines in good yields.     

A simple microwave-assisted preparation of 2-bromo-1-alkenes from 1-alkynes using the LiBr-TMSCl-TEAB reagent system

2-Bromo-1-alkenes are cleanly and conveniently generated in good yields and selectivities via microwave-assisted hydrobromination of 1-alkynes using a combination of lithium bromide (LiBr), chlorotrimethylsilane (TMSCl), and tetraethylammonium bromide (TEAB) in acetonitrile (MeCN).     

Disulfides by reduction of thiosulfunic S-esters

Disulfides are smoothly prepared from thiosulfonic S-esters by chlorotrimethylsilane and sodium iodide. In addition, thiosulfonic S-esters have been shown to be probable intermediates in other already known reactions leading to disulfides.     

A Convenient Synthesis of 4,5-Diaryl-1,8-Dihalo-3,6-Dioxaoctanes

A kind of useful precursors for the construction of vicinal diaryl-substituted macrocycles, 4,5-diaryl-1,8-dihalo-3,6-dioxaoctanes, was readily produced by reductive coupling of aromatic carbonyl compounds with 2-haloethanols in the presence of tin powder and chlorotrimethylsilane in moderate to good yields by a one-pot procedure.