Heterogeneous Thiocyanation of Benzylic Alcohols and Silyl and THP Ethers,and Deprotection of Silyl and THP-Ethers by [PCl3-n(SiO2)n] (Silphos)

Silicaphosphite (silphos), [PCl_3-n(SiO₂)_n], as a heterogeneous phosphorous compound, catalyzes the thiocyanation of benzylic alcohols and silyl and THP ethers in the presence of I₂ and NH₄SCN in refluxing CH₃CN. The produced silphos oxide byproduct can be easily separated by a simple filtration. Silphos is also used for the efficient and selective deprotection of silyl and THP-ethers to their corresponding alcohols.     

Solvent-Free Esterification of Carboxylic Acids and Alcohols in the Presence of Silphos [PCl3-n(SiO2)n] as a Heterogeneous Phosphine Reagent

An efficient solvent-free method for the preparation of esters from various aromatic and aliphatic acids with primary, secondary, and tertiary alcohols using a heterogeneous phosphine reagent, silphos [PCl_3-n(SiO₂)_n], in good yields is reported.     

One‐Pot,Four‐Component Reaction of Aryl Aldehydes,Aryl Ketones,Phosphorus Trichloride,and Acetonitrile Catalyzed by Acetyl Chloride: Synthesis of β‐Acetamido Ketones

The one‐pot, four‐component reaction of aryl aldehydes, aryl ketones, phosphorus trichloride, and acetonitrile, catalyzed by acetyl chloride, affords β‐acetamido ketones in good to excellent yields. Silicaphosphine (silphos), [P(Cl)_3‐n(SiO₂)_n], can also be used effectively as a solid‐supported reagent instead of phosphorus trichloride.