Benzylation of alcohols and other substrates under thermal conditions translates smoothly from conventional heating into MW-assisted organic synthesis (MAOS). Reactions times are decreased from hours to minutes while good to excellent yields are maintained. MW heating should be considered for benzylation of high-value substrates using the title reagent.

Broadly applicable palladium-catalyzed heteroarene benzylation reactions are described with a focus on the most challenging heterocyclic classes under traditional benzylation techniques such as sulfur-containing heterocycles and those bearing functional groups that would be incompatible with reactions requiring Lewis acids and/or strong bases.

Reactions of 2-amino-aryl alcohols with beta-ketoesters catalyzed by a catalytic amount of FeCl3 via tandem benzylation-cyclization produce the corresponding 3-quinolinecarboxylic esters in good to high yields. Extending this methodology to propargylation-cyclization, 2-nitrophenyl propargyl alcohols with beta-ketoesters catalyzed by FeCl3 and SnCl2 also produce the 4-alkyne-3-quinolinecarboxyl...

Mercaptobenzoic acid-palladium(0) complexes show high catalytic activity for S-benzylation with benzylic alcohols via the (η(3)-benzyl)palladium(II) cation in water. Notably, these palladium(0) complexes could play an important role in formation of active (η(3)-benzyl)palladium(II) cation complexes followed by S-benzylation. Hammett studies on the rate constants of S-benzylation by various subs...

A strategy for selective mono-, di- and tri-O-methylation of kaempferol, predominantly on the basis of selective benzylation and controllable deacetylation of kaempferol acetates, was developed. From the selective deacetylation and benzylation of kaempferol tetraacetate (1), 3,4',5,-tri-O-acetylkaempferol (2) and 7-O-benzyl-3,4'5,-tri-O-acetylkaempferol (8) were obtained, respectively. By contr...

A palladium-catalyzed benzylation of α-branched aldehydes has been developed using benzyl methyl carbonates. The method gives access to congested quaternary centers in the vicinity of one of the most sensitive carbonyl functionalities and displays unprecedented generality with respect to both coupling partners. Evidence for the direct involvement of a Pd-η(3)-benzyl intermediate is provided. Ex...

Phenolic compounds can be efficiently O-methylated with tetramethylammonium chloride in diglyme or polyethyleneglycol (PEG) at temperatures of 150-160 °C and in the presence of either K2CO3 or NaOH. When applying benzyltrimethylammonium chloride as a reagent, the benzylation and methylation of phenols occurs, with the benzylation product always predominating. With allyl-substituted phenols as s...

A series of functionalized 4H-chromenes have been constructed by using a novel FeCl(3)-catalyzed benzylation-cyclization tandem reaction.

An efficient BF3·Et2O-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.

Total syntheses of the cytotoxic Leucetta-derived 2-aminoimidazoles, naamine G and naamidine H, have been accomplished using a position selective metalation-benzylation sequence with a 4,5-diiodoimidazole derivative.