Nitriles, unsaturated, rhodium-catalyzed

Rhodium-Catalyzed Asymmetric Hydroformylation of Unsaturated Nitriles... 

Alternatively, iron- or rhodium-catalyzed hydrodecyanation reaction is proposed to be initiated by the C-CN activation of aromatic and aliphatic nitriles with silylmetal species to give iminoacylmetal intermediates and then sUylisonitrile metal complexes, which produce decyanated products and silyl cyanides upon the reaction with hydrosUanes to reproduce the catalyticaUy active silylmetal intermediates (Scheme 7). Irradiation is required to generate coordinatively unsaturated iron complexes (Scheme 8) [45, 46]. A similar reaction mechanism also operates... 

DSM reported that the asymmetric hydroformylation of unsaturated nitriles (Scheme 12.72) to provide a potential route to (/ )-4-amino-2-methyl-l-ol (180), which is a key intermediate for TAK-637 (181), a new Tachykinin NK, receptor antagonist, developed by Takeda (Scheme 12.73). Rhodium-BINAPHOS (4 equiv) has catalyzed the asymmetric hydroformylation of but-3-enenitrile (allyl cyanide) with regioselectivity of 72/28 (b/1) and 66% ee at 73% conversions.227... 

Cationic rhodium(I)/chiral biaryl bisphosphine complexes are suitable for the enantioselective [2-I-2-1-2] cycloaddition reactions between electron-rich alkynes and electron-deficient unsaturated compounds (alkynes, nitriles, and isocyanates). Alkynylcarbonyl compounds, alkynylphosphonates, and alkynylphosphine oxides are the best-suited electron-deficient unsaturated compounds for these catalysts. These complexes are also able to catalyze the highly enantioselective synthesis of axially chiral anilides and bezamides. 

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