Metal cyanides nucleophilic additions

Heterocyclic structures analogous to the intermediate complex result from azinium derivatives and amines, hydroxide or alkoxides, or Grignard reagents from quinazoline and orgahometallics, cyanide, bisulfite, etc. from various heterocycles with amide ion, metal hydrides,or lithium alkyls from A-acylazinium compounds and cyanide ion (Reissert compounds) many other examples are known. Factors favorable to nucleophilic addition rather than substitution reactions have been discussed by Albert, who has studied examples of easy covalent hydration of heterocycles. 

The Strecker reaction [1] starting from an aldehyde, ammonia, and a cyanide source is an efficient method for the preparation of a-amino acids. A popular version for asymmetric purposes is based on the use of preformed imines 1 and a subsequent nucleophilic addition of HCN or TMSCN in the presence of a chiral catalyst [2], Besides asymmetric cyanations catalyzed by metal-complexes [3], several methods based on the use of organocatalysts have been developed [4-14]. The general organocatalytic asymmetric hydrocyanation reaction for the synthesis of a-amino nitriles 2 is shown in Scheme 5.1. 

Simple /V-a Iky I a ted imines, e.g. V-methylaldimine (18, R1 = aryl, alkyl), undergo nucleophilic addition using a masked acyl cyanide reagent [19, where the masked group = —C(CN)2—O—] with C-C bond formation to give an a-amido ester (20).78 This mild conversion does not require pre-activation (i.e. incorporation of an activating group in the substrate) or post-activation (i.e. Brpnsted or Lewis acid, or metallic species). 

Nucleophilic addition of the metal-stabilized pyrrolium complexes is readily achieved with borohydride and cyanide ion. The scope of this reactivity is bracketed by the diminished electrophilicity of the iminium carbons and the acidity of the ammine ligands, which prevents the use of strongly basic nucleophiles. Competing deprotonation of the acidic pyrrolium ring protons is observed primarily only with 3//-pyrrolium complexes or when bulky nucleophiles are used. 

In addition to metal catalysts, organocatalysts could also be used in asymmetric cyanation reactions. Chiral Lewis bases, modified cinchona alkaloids, catalyzed asymmetric cyanation of ketones by using ethyl cyanoformate as the cyanide source (Scheme 5.34)." Similar to metal-catalyzed reactions, ethyl cyanoformate was first activated by chiral Lewis bases to form active nucleophiles. Various acyclic and cyclic dialkyl ketones were transformed into the desired products. Because of using... 

A variety of basic (nucleophilic) initiators have been used to initiate anionic polymerization [Bywater, 1975, 1976, 1985 Fontanille, 1989 Hsieh and Quirk, 1996 Morton, 1983 Morton and Fetters, 1977 Quirk, 1995, 1998, 2002 Richards, 1979 Szwarc, 1983 Young et al., 1984]. These include covalent or ionic metal amides such as NaNFU and LiN(C2H5)2, alkoxides, hydroxides, cyanides, phosphines, amines, and organometallic compounds such as n-C4H9Li and <)>MgBr. Initiation involves the addition to monomer of a nucleophile (base), either a neutral (B ) or negative (B ) species. 

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