Standard reaction conditions for the desilylation of acetylated furanoside (riboside, arabinoside and xyloside) derivatives facilitate acyl migration. Conditions which favour intramolecular and intermolecular mechanisms have been identified with intermolecular transesterifications taking place under mild basic conditions when intramolecular orthoester formations are disfavoured. In acetyl ribos...

The most commonly available 2' hydroxyl protecting group used in the synthesis of oligoribonucleotides is the tert-butyldimethylsilyl moiety. This protecting group is generally cleaved with 1 M tetrabutylammonium fluoride (TBAF) in tetrahydrofuran (THF). The efficiency of this reaction was tested on ribonucleotidyldeoxythymidine dinucleotides (AT, CT, GT, and UT). We have found that the efficie...

A reaction-based chemosensor (AF-1) was designed, synthesized and applied as an optical approach for quantitative measurement of F(-) in MeCN. In the presence of F(-), selective fluoride-assisted desilylation instantly gave colorimetric and fluorogenic signals, providing a dual-optical channel for the detection of F(-). (1)H NMR titration was carried out to investigate the desilylation process,...

A copper-catalyzed asymmetric [3+2] cycloaddition of 3-trimethylsilylpropargylic esters with either β-naphthols or electron-rich phenols has been realized and proceeds by a desilylation-activated process. Under the catalysis of Cu(OAc)2⋅H2O in combination with a structurally optimized ketimine P,N,N-ligand, a wide range of optically active 1,2-dihydronaphtho[2,1-b]furans or 2,3-dihydrobenzofura...

Michaelis-Arbuzov reactions of S-aryl disulfide derivatives of 3'-thiothymidine or 5'-thioadenosine with tris(trimethylsilyl) phosphite proceeded in high yields to the corresponding phosphorothiolate monoesters. Subsequent hydrolytic desilylation and phosphate coupling were effected in one-pot using liquid-assisted grinding in a vibration ball mill. Novel 3',5'- and 5',5'-pyrophosphorothiolate-...

The addition of AlCl3 to four-coordinate boranes of the general formula (C-N-chelate)BCl2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl]+. The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl3 were sufficie...

The current realm of Lewis acid-promoted propargylsilane additions to carbonyl groups2 may be subdivided into two mechanistically distinct categories: (i) additions proceeding via a desilylation pathway;3 (ii) additions involving a [1,2]-silyl shift.4 Process (i) generates allenic alcohols and is most common when nonbulky silyl groups such as TMS are employed,3 whereas the latter scenario has b...

1,1’-(ethane-1,2-diyl)dipyridinium bistribromide (edpbt) was used as a chemoselective and effective organocatalyst for the silylation of hydroxyl groups as well as desilylation of trimethylsilyl ethers under mild conditions at room temperature with good to excellent yields.

1,1’-(Ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) was used as a chemoselective and effective organocatalyst for the silylation of hydroxyl groups as well as desilylation of trimethylsilyl ethers under mild conditions at room temperature with good to excellent yields.