Trimethylsilylation of Hydroxyl Group with 1,1,1,3,3,3‐Hexamethyldisilazane (HMDS) Catalyzed by Tribromomelamine (TBM)

Tribromomelamine (TBM) can be used as a novel catalyst for the trimethylsilylation of alcohols and phenols with 1,1,1,3,3,3‐hexamethyldisilazane (HMDS). A wide variety of hydroxyl groups were selectively protected in CH₂Cl₂/CH₃CN under mild conditions.     

Chemoselective Protection of Hydroxyl Groups and Deprotection of Silyl Ethers

Summary.  Trimethylsilylation of alcohols and phenols is carried out using hexamethyldisilazane and LiClO₄ under microwave irradiation and neutral conditions. The deprotection of silyl ethers is carried out similarly using natural kaolinitic clay and a few drops of water. Received March 1, 2001. Accepted (revised) April 17, 2001     

Chemoselective trimethylsilylation of alcohols catalyzed by saccharin sulfonic acid

Abstract  Saccharin sulfonic acid was easily prepared by the reaction of saccharin with neat chlorosulfonic acid at room temperature. This reagent is efficiently able to catalyze the chemoselective trimethylsilylation of alcohols with hexamethyldisilazane in the presence of amines and thiols. Graphical abstract        

Silica Sulfate,an Efficient Catalyst for the Trimethylsilylation of Alcohols

An easy method for the preparation of trimethylsilyl ethers from alcohols and 1,1,1,3,3,3‐hexamethyl‐disilazane (HMDS) using silica sulfate as a catalyst under mild conditions in excellent yields is described.     

Sodium Hydrogen Sulfate in Poly(ethylene glycol). An Efficient Recyclable System for the Deprotection of 1,1-Diacetates

Summary. Poly(ethylene glycol) was used as the solvent for selective deprotection of 1,1-diacetates (acylals) with easy recyclability of solvent and sodium hydrogen sulfate catalyst. This method is high yielding, fast, clean, safe, and therefore very suitable for practical organic synthesis.     

Efficient and Selective Oxidative Deprotection of Trimethylsilyl Ethers Using Supported Potassium Ferrate Under Microwave Irradiation

Primary and secondary trimethylsilyl ethers are efficiently and rapidly converted to their corresponding carbonyl compounds with supported potassium ferrate under microwave irradiation in solventless system.     

Novel and Highly Effective Method for the Trimethylsilylation of Alcohols and Phenols with Hexamethyldisilazane (HMDS), Catalyzed by I2 Generated in situ Using Fe(NO3)3⋅9 H2O/NaI under Heterogeneous and Neutral Conditions

Structurally diverse alcohols and phenols were trimethylsilylated in a clean and efficient reaction with hexamethyldisilazane (HMDS) based on the use of I₂ generated in situ from Fe(NO₃)₃?9 H₂O/NaI. The reaction occurs very rapid in good‐to‐high yield in CH₂Cl₂ at room temperature, and the use of toxic and corrosive molecular I₂ is avoided.     

Fe(HSO4)3 Promoted Trimethylsilylation of Alcohols and Phenols in Solution and Under Solvent-Free Conditions

Summary. Alcohols and phenols are efficiently converted to their corresponding trimethylsilyl ethers with hexamethyldisilazane (HMDS) in the presence of Fe(HSO₄)₃ in solution and under solvent-free conditions.     

Ethylenebis(N‐Methylimidazolium) Chlorochromate (EBMICC): A New Selective and Mild Reagent for Oxidation of Alcohols,Hydroquinones and Trimethylsilyl Ethers

The ethylenebis(N‐methylimidazolium) chlorochromate was prepared by addition of N‐methylimidazole to 1,2‐dibromoethane to form the corresponding dibromide salt and subsequent treatment of this salt with CrO₃ in 6N HCl solution. It is a stable yellow‐orange solid which selectively oxidized benzylic and allylic alcohols, hydroquinones and trimethylsilyl ethers in refluxing acetonitrile. Oxidation of alcohols was also examined under solvent‐free conditions and showed much better yields of the corresponding carbonyls in a very short reaction time when compared with the conventional method.     

Oxidative Deprotection Of Trimethylsilyl and Tetrahydropyranyl Ethers and Ethylene Acetals With Benzyltriphenylphosphonium Peroxomonosulfate in the Presence of Bismuth Chloride Under Non-Aqueous Conditions

Abstract

Benzyltriphenylphosphonium peroxomonosulfate (BnPh₃P⁺HSO₅ ^?) (1) is used as a new reagent for oxidative deprotection of trimethylsilyl and tetrahydropyranyl ethers and ethylene acetals to afford carbonyl compounds in refluxing acetonitrile in the presence of bismuth chloride.     

Efficient Trimethylsilylation of Alcohols and Phenols with HMDS in the Presence of a Catalytic Amount of 1,3‐Dibromo‐5,5‐Dimethylhydantoin (DBDMH) as a Safe and Cheap Industrial Chemical

1,3‐Dibromo‐5,5‐dimethylhydantoin (DBDMH) is found to be an effective catalyst for trimethylsilylation various alcohols and phenols with hexamethyldisilazane (HMDS) in dichloromethane at room temperature.     

Manganese-Catalyzed Chemoselective Coupling of Secondary Alcohols,Primary Alcohols and Methanol

Herein, we report a manganese-catalyzed three-component coupling of secondary alcohols, primary alcohols and methanol for the synthesis of β,β-methylated/alkylated secondary alcohols. Using our method, a series of 1-arylethanol, benzyl alcohol derivatives, and methanol undergo sequential coupling efficiently to construct assembled alcohols with high chemoselectivity in moderate to good yields. Mechanistic studies suggest that the reaction proceeds via methylation of a benzylated secondary alcohol intermediate to generate the final product.     

Vanadium(III) Chloride (VCl3): Efficient Reagent for the Introduction of Tetrahydrofuran‐Based Acetal Protecting Groups for Alcohols

Treatment of different types of alcohols with tetrahydrofuran (THF) in the presence of VCl₃ and CCl₄ smoothly afforded the corresponding THF‐based acetals in excellent yields. The reaction is fast at room temperature, and several functional groups are tolerated, with no racemization being observed. A radical mechanism, based on Cl₃C^. as the active species, is proposed for this novel kind of transformation, which complements the classical tetrahydro‐2H‐pyran‐2‐yl (THP) protocol.     

1,3–Dichloro‐5,5–Dimethylhydantoin (DCH) and Trichloromelamine (TCM) as Efficient Catalysts for the Chemoselective Trimethylsilylation of Hydroxyl Group with 1,1,1,3,3,3–Hexamethyldisilazane (HMDS) Under Mild Conditions

A highly convenient method for the trimethylsilylation of alcohols and phenols via treatment by hexamethyldisilazane in the presence of 1,3–dichloro‐5,5–dimethylhydantoin (DCH) and/or trichloromelamine (TCM) as a catalyst has been developed. A wide variety of hydroxyl groups were selectively protected in CH₂Cl₂/CH₃CN under mild conditions.     

Trimethylsilylation of Alcohols and Phenols using KBr as an Efficient and Reusable Catalyst

KBr acts as an efficient and reusable catalyst for the selective and efficient trimethylsilylation of benzylic, primary and secondary aliphatic alcohols and phenols with hexamethyldisilazane. All reactions were performed at room temperature under mild and completely heterogeneous conditions in good to high yields.     

Efficient Method for Tetrahydropyranylation of Alcohols and Phenols and Deprotection of THP Ethers using H14[NaP5W30O110] as a Green Catalyst

A simple and effective method for tetrahydropyranylation of alcohols and phenols and the regeneration of THP ethers using a catalytic amount of H₁₄[NaP₅W₃₀O₁₁₀] is reported.     

Melamine Trisulfonic Acid (MTSA): A New Efficient Catalyst for the Chemoselective Methoxymethylation of Alcohols

Melamine trisulfonic acid, which is easily prepared by the reaction of melamine with neat chlorosulfonic acid, is able to efficiently catalyze the chemoselective methoxymethylation of alcohols with dimethoxymethane (DMM). All reactions were performed under mild and completely heterogeneous reaction conditions in good to high yields.     

H5IO6/KI: A New Combination Reagent for Iodination of Aromatic Amines,and Trimethylsilylation of Alcohols and Phenols through in situ Generation of Iodine under Mild Conditions

A simple method for the in situ generation of iodine using H₅IO₆/KI has been developed, and its application in silylation of OH group and iodination of aromatic amines is described.     

Chemoselective Oxidation of Benzylic Alcohols and Hydroquinones with bis-(2,4,6-Trimethylpyridinium) Dichromate (BTMPDC) as an Efficient and New Oxidizing Agent

A simple, efficient, and chemoselective oxidation of benzylic alcohols to the corresponding aldehydes and ketones and also hydroquinones to the benzoquinones using bis-(2,4,6-trimethylpyridinium) dichromate (BTMPDC) in acetonitrile is described. A good range of primary and secondary benzylic alcohols and a limited range of hydroquinones were selectively oxidized under reflux conditions in reasonable yields.     

A Mild and Efficient Method for Chemoselective Silylation of Alcohols Using Hexamethyldisilazane in the Presence of Silica Chloride

Reaction of alcohols with hexamethyldisilazane in the presence of silica chloride provides efficiently the corresponding trimethylsilyl ethers. This system discriminates absolutely amines and thiols from alcohols.