Nitrile group stereoselective transformation

MBH acetates can be stereoselectively transformed into ( )- or (Z)-allyl amides, in case of MBH adducts derived from acrylates or acrylonitriles, by reaction with nitriles in the presence of CH3SO3H or Amberlyst-15 as a catalyst. In addition, 2-benzazepine derivatives 296 have been prepared from some MBH adducts containing an electron-rich aryl group via a convenient one-pot procedure involving tandem construction of C-N and C-C bonds (Scheme 3.125). ... 

By hydrogenation of the nitrile group of a-sulfonyloxynitriles 22 the corresponding amino compounds 24 are formed primarily, which immediately react intramolecularly to give the aziridines 25 under inversion of configuration (Scheme 15) [58]. Analogous to chiral ox-iranes, chiral aziridines are of interest for numerous stereoselective transformations [59]. 

Addition of CN Anion Stereoselective addition of the CN-group to nitrones has received considerable attention for the synthesis of optically active a-hydroxyamino nitriles which can be further transformed into a-hydroxyamino acids and a-amino acids. Me SiCN (TMSCN), Et2AlCN, BU4NCN, and LiCN... 

The vinyltin 45 also can be used as an unsaturated system for C-H transformation of nitriles Id and le producing the corresponding alkylative dimerization products of the vinyl group, 1,4-disubstituted butene derivatives 46 (Scheme 10) [14]. The reaction proceeds in a stereoselective fashion to give the trans isomer selectively. Malono-nitrile does not react with the vinyltin under the reaction conditions. 

On the other hand, oxidation of 161 with dimethyl dioxirane gave a 1 9 mixture of diols 165 and 166 (Scheme 31). Surprisingly and inexplicably the major product 166 results from attack on the double bond face syn to the arylsulfonyl moiety. Diol 166 could be converted to monoacetate 167 which underwent stereoselective alkylation with allyl trimethylsilane to yield 168. Similarly, acetate 167 could be converted to a single nitrile 169. Both of these transformations involve axial attack anti to the arylsulfonyl group on an intermediate N-sulfon-ium iminium ion. 

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