Rhodium cyanation

Cyanation of acetals. This reaction has been effected with CNSi(CH3)3 and a Lewis acid catalyst (11, 150). It can also be effected under neutral conditions with several transition metal catalysts, in particular, with [Rh(COD)Cl]2, CoCl2, and NiCl2, listed in the order of decreasing activity. Based upon this reaction, Mukai-yama et al.1 have examined the use of the combination of cyanotrimethylsilane and the rhodium catalyst for general activation of silyl enol ethers or ketene silyl acetals. 

Other isocyanate syntheses that have recently been reported include several well-known reactions. One area which has attracted considerable attention is that of the direct production of isocyanates by the carbonylation of nitro-arenes. Both mono- and di-isocyanates are claimed to have been produced using various catalysts palladium, rhodium, and iron compounds often being cited. Other preparative reactions for isocyanates which have appeared in the literature include the acid catalysed hydrolysis of isocyanide dihalides and the reaction between alkyl halides and alkali-metal cyanates, although the latter has been given a modern flavour by the use of a polymer-supported reagent. ... 

Keywords Carbocyanation C-CN activation Copper Cross-coupling Cyanation Hydrodecyanation Nickel Rhodium... 

Intramolecular cyanation of a styrene by a rhodium(I)-catalysed N-CN cleavage reaction has been reported, showing atom economical alkene cyanation (Scheme 153). ... 

Hong, X. Wang, H. Qian, G. Xu, B. Rhodium-catalyzed direct C—H bond cyanation of arenes with isocyanide. J. Org. Chem. 2014,79, 3228-3237. 

Rhodium-Catalyzed Cyanation of Aryl- and Vinylboronic Acids. The rhodium-catalyzed electrophilic cyanation of aryl-boronic acids has been developed to afford various benzonitriles in good yields. Interestingly, among a variety of electrophilic cyanation agents 1 and 9-12 examined in this study, the title... 

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