Amides with organometallic

Nitriles are similar in some respects to carboxylic acids and are prepared either by SN2 reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar C=N bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with organometallic reagents to yield ketones. 

For a list of preparations of ketones by the reaction of organometallic compounds with carboxylic esters, salts, anhydyrides, or amides, with references, see Ref. 568, pp. 685, 693. 

The new silazane 5 may be reacted with activated metals, organometallic compounds or simple metal amides, or may first be transformed to its lithium salt and then reacted with metal(II) chlorides [11]. In all these cases, metal derivatives of 5 are obtained with the general formula j [Mc (/BuO)Si 9N(9M, which have no further base coordinated to the metal. So far we have synthesized amides with M = Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ba, all elements in oxidation state +2. X-ray structure determinations have been performed on the calcium, manganese, iron, zinc, and barium derivatives. 

Unlike with sodium borohydride (see Section 11.01.5.2), pyrrolizin-3-one 2 reacts with lithium aluminohydride mainly as an amide. No conjugate addition occurs, and only the reductive lactam cleavage takes place to give stereoselectively the (Z)-allylie alcohol 77. Similarly, benzo-annulated pyrrolizin-3-one 17 gives the corresponding benzylic alcohol 78. The same reactivity was observed with organometallics such as methyllithium which gives exclusively the tertiary (Z)-allylic alcohol 79 (Scheme 7). 

The Conversion of Anhydrides, Carboxylic Esters, or Amides to Ketones with Organometallic Compounds1659 Alkyl-de-acyloxy-substitution... 

Mechanism 21-13 Hydride Reduction of an Ester 1015 Mechanism 21-14 Reduction of an Amide to an Amine 1016 21-9 Reactions of Acid Derivatives with Organometallic Reagents 1017 Mechanism 21-15 Reaction of an Ester with Two Moles of a Grignard Reagent 1018... 

Bambirra, S., Boot, S.J., Tazelaar, C.GJ. etal. (2004) Yttrium alkyl complexes with triamino-amide ligands. Organometallics, 23, 1891. 

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