16133-88-3

Upstream product

• 100-53-8 phenylmethanethiol 
• 824-94-2 p-methoxybenzyl chloride 
• 100-87-8 Benzylsulfonic acid 
• 1515-81-7 1-methoxy-4-(methoxymethyl)benzene 
• 105-13-5 4-Methoxybenzyl alcohol 
• 27691-43-6 1-(benzylsulphanyl)-4-Nitrobenzene 
• 6258-60-2 p-methoxybenzylmercaptan 
• 54879-64-0 N-[(4-methoxyphenyl)methyl]-4-methylbenzenesulfonamide 

Downstream Products

• 100-52-7 benzaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 
• 1410785-98-6 benzyl 4-methoxybenzyl sulfone 
• 1694-19-5 E-1-(phenyl)-2-(4'-methoxyphenyl)ethene 
• 30749-71-4 1-((benzylsulfinyl)methyl)-4-methoxybenzene 

Relevant academic research and scientific papers

Discriminating non-ylidic carbon-sulfur bond cleavages of sulfonium ylides for alkylation and arylation reactions

A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.

Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid

The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions.

Silyl trifluoromethanesulfonate-activated para-methoxybenzyl methyl ether as an alkylating agent for thiols and aryl ketones

Para-Methoxybenzyl methyl ether acts as an alkylating agent for thiols in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine base in good yields (58-96%). Aryl ketones are alkylated under similar conditions, probably through an eno

Selective benzylic and allylic alkylation of protic nucleophiles with sulfonamides through double Lewis acid catalyzed cleavage of sp3 carbon-nitrogen bonds

The acid-catalyzed benzylic and allylic alkylation of protic nucleophiles is fundamentally important for the formation of carbon-carbon and carbon-heteroatom bonds, and it is a formidable challenge for benzylic and allylic amine derivatives to be used as the alkylating agents. Herein we report a highly efficient benzylic and allylic alkylation of protic carbon and sulfur nucleophiles with sulfonamides through double Lewis acid catalyzed cleavage of sp3 carbon-nitrogen bonds at room temperature. In the presence of a catalytic amount of inexpensive ZnCl2-TMSCl (TMSCl: chlorotrimethylsilane), 1,3-diketones, β-keto esters, β-keto amides, malononitrile, aromatic compounds, thiols, and thioacetic acid can couple with a broad range of tosylactivated benzylic and allylic amines to give diversely functionalized products in good to excellent yields and with high regioselectivity. Furthermore, the cross-coupling reaction of 1,3-dicarbonyl compounds with benzylic propargylic amine derivatives has been successfully applied to the one-step synthesis of polysubstituted furans and benzofurans.

Singlet oxygen promoted carbon-heteroatom bond cleavage in dibenzyl sulfides and tertiary dibenzylamines. Structural effects and the role of exciplexes

(Chemical Equation Presented) The C-heteroatom cleavage reactions of substituted dibenzyl sulfides and substituted dibenzylcyclohexylamines promoted by singlet oxygen in MeCN have been investigated. In both systems, the cleavage reactions (leading to benzaldehyde and substituted benzaldehyde) were slightly favored by electron-withdrawing substituents with ρ values of +0.47 (sulfides) and +0.27 (amines). With dibenzyl sulfides, sulfones were also obtained whereas sulfoxide formation became negligible when the reactions were carried out in the presence of a base. Through a careful product study for the oxidation of dibenzyl sulfide, in the presence and in the absence of Ph 2SO, it was established that sulfone and cleavage product (benzaldehyde) do not come by the same route (involving the persulfoxide and the hydroperoxysulfonium ylide) as required by the generally accepted mechanism (Scheme 1) for C-heteroatom cleavage reactions of sulfides promoted by singlet oxygen. On this basis and in light of the similar structural effects noted above it is suggested that dibenzyl sulfides and dibenzylamines form benzaldehydes by a very similar mechanism. The reaction with singlet oxygen leads to an exciplex that can undergo an intracomplex hydrogen atom transfer to produce a radical pair. With sulfides, collapse of the radical pair leads to an α-hydroperoxy sulfide than can give benzaldehyde by an intramolecular path as described in Scheme 3. With amines, the radical pair undergoes an electron-transfer reaction to form an iminium cation that hydrolyzes to benzaldehyde. From a kinetic study it has been established that the fraction of exciplex converted to aldehyde is ca. 20% with sulfides and ca. 7% with amines.

Direct synthesis of thioethers from sulfonyl chlorides and activated alcohols

An efficient, safe one-pot synthesis of thioethers from aromatic sulfonyl chlorides and activated alcohols has been developed under non-aqueous conditions.