Cyanomethylation 558 Subject

In the reaction of 88 with /(-phenethyl bromide, l-phenethyl-3-phenylpropyl methyl sulfoxide and bis-3-phenylpropyl sulfoxide, besides 3-phenylpropyl methyl sulfoxide are obtained118. Sulfoxides, bearing a /1-hydrogen to the sulfmyl function, give olefins upon thermolysis. Utilizing this reaction, Trost and Bridges120 alkylated benzyl phenyl sulfoxide, 3,4-methylenedioxybenzyl phenyl sulfoxide, phenylthiomethyl phenyl sulfoxide, phenylsulfinylmethyl phenyl sulfoxide and cyanomethyl phenyl sulfoxide with alkyl, allyl and benzyl halides and subjected these sulfoxides to thermolysis, obtaining olefins in one-pot processes. 

Cyanomethylation. Carbonyl compounds and imines are subject to cyanomethylation by Me3SiCH2CN with tris(2,4,6-trimethoxyphenyl)phosphine as catalyst. ... 

Oxidative cyanation. The methyl group of substituted ArNMe2 is subjected to catalyzed autooxidation, and the intermediate radicals can be intercepted with PhCOCN, affording the A-cyanomethyl derivatives. 

Secondary Dios-amides can also be subjected to the Mitsunobu alkylation utilizing CMBP. Although the reaction can be expected to be promoted with satisfactory results by cyanomethyl-enetrimethylphosphorane (CMMP), which is a more highly reactive Mitsunobu reagent than CMBP, the commercially available CMBPpossesses sufficient reactivity to afford tertiary Dios-amide in excellent yield (eq 11). 

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