Benzoyl cyanide, selective benzoylation

In connection with the synthesis of C-glycosyl compounds, Moffatt and coworkers182 developed the selective debenzoylation of 2,3,5-tri-0-benzoyl-/3-D-ribofuranosyl cyanide, which had been reported earlier163 reaction in methanolic ammonia-chloroform at 0° gave the crystalline 5 -0-benzoyl derivative in 83% yield, without recourse to chromatography. 

Benzoyl cyanides are excellent reagents for selective N-benzoylation of amino alcohols. 

Among the processes used for the formation of polyolefins, the longest-known but least selective one is free radical polymerization. A free radical species X produced e.g. by thermolysis of benzoyl peroxide or by photolysis of azabisisobutyronitrile (AIBN) - can react with the double bond of a vinyl derivative H2C=CHR to form a new radical of the type XCH2-CHR which can then add another H2C=CHR unit repetition of this process leads to polyolefin formation (Figure 2, top). This process works best for vinyl derivatives with unsaturated side groups, which provide resonance stabilization for an adjacent radical centre, e.g. with vinyl and acrylic esters, vinyl cyanides and vinyl chloride and with styrene and 1,3-dienes. It is extensively used in the emulsion polymerization of vinylic and acrylic derivatives and in the light-induced formation of photoresists for the nanofabrication of semiconductor chips and integrated electronic circuits. 

The natural product tremuloidin (20) has been synthesized from salicin (18) by selective benzoylation of the partly protected intermediate 19 by use of benzoyl cyanide, followed by deprotection. A practical one-pot technique for the conversion of methyl a-D-gluco- and -manno-pyranoside to their 2,3,4-tri-0-(4-methylbenzoates) has been described. ... 

Benzoyl cyanide has been found to be superior to AT-benzoylimidazole as a selective benzoylating reagent for carbohydrates. Thus, mono-benzoylation of... 

Benzoyl cyanide in the presence of triethylamine has been used for the rapid ca. 30 min) perbenzoylation of aldoses,and benzoyltetrazole has been shown to be an excellent benzoylating reagent for the hydroxy-groups of most common nucleosides some selectivity between primary and secondary hydroxy-groups could be achieved. The allylic hydroxy-group of several unsaturated pyranosides... 

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