Amides organometallics

Garcia-Alvarez R, Diez J, Crochet P, Cadiemo V (2011) Arene-rathenium(ll) complexes containing inexpensive tris(dimethylamino)phosphine Highly efficient catalysts for the selective hydration of nitriles to amides. Organometallics 30 5442... 

Gnanamgari D, Crabtree RH (2009) Terpyridine ruthenium-catalyzed one-pot conversion of aldehydes into amides. Organometallics 28 922... 

Kahnes M, Gorls H, Gonzalez L, Westerhausen M (2010) Synthesis and catalytic reactivity of Bis(alkylzinc)-hydride-di(2-pyridylmethyl)amides. Organometallics 29 3098-3108. doi 10. 

The first organometallic compounds we encountered were compounds of the type RC=CNa obtained by treatment of terminal alkynes with sodium amide m liquid ammo nia (Section 9 6)... 

Bell and Hall have incorporated an organometallic unit into a crown by using the ferrocenyl unit as part of the ring or as a third strand. The unit is incorporated either as the 1,1 -diformylferrocene or the corresponding acid. In the former case, the bis-imine is prepared and reduced to give the saturated crown (see structure 24). In the latter case, the acid is converted into its corresponding chloride and thence into the diamide by reaction with a diamine. Diborane reduction affords the saturated amino-crown. Structure 24 could be prepared by either of these methods but the dialdehyde approach was reported to be poor compared to the amide approach which afforded the product in ca. 60% yield . 

In recent years this simple picture has been completely transformed and it is now recognized that the alkali metals have a rich and extremely varied coordination chemistry which frequently transcends even that of the transition metals. The efflorescence is due to several factors such as the emerging molecular chemistry of lithium in particular, the imaginative use of bulky ligands, the burgeoning numbers of metal amides, alkoxides, enolates and organometallic compounds, and the exploitation of multidentate... 

Organometallic reagents and alkali metal amides can react via a cyclic transition state (Section II, B, 5) beginning with electrophilic attack at the most basic ring-nitrogen. As a result, sodamide (in dimethylaniline, 145°, 2 hr) yields the 4-amino derivatives (40% yield S)) methyl- or phenyl-magnesium iodides give the 4-adduct quantitatively.s ... 

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. 

The most common reactions of carboxylic acid derivatives are substitution by water (hydrolysis) to yield an acid, by an alcohol (alcoholysis) to yield an ester, by an amine (aminolysis) to yield an amide, by hydride ion to yield an alcohol (reduction), and by an organometallic reagent to yield an alcohol (Grignard reaction). 

In the case of the amide 11 (R = CI13) derived from 2-oxopropanoic amid and amine G the chelation-controlled product is predominantly formed with all organometallic reagents. No reversal of the stereochemistry is observed, presumably for the same steric reason as with the corresponding pyruvic amides derived from amines E and F. 

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 Conversion of Organometallic Compounds to Ketones, Aldehydes, Carboxylic Esters, or Amides... 

Other organometallic compounds add to isocyanates. Vinyltin reagents lead to conjugated amides. ... 

Optically pure a-amino acids can be converted to 1,2-diamines by a route that involves the preliminary formation of N-protected a-aminonitriles through the intermediate amides. The addition of organometallic reagents to these a-aminonitriles gives a-amino ketimines, which are then reduced in situ to 1,2-diamines. However, this route has been scarcely applied to acychc a-aminonitriles. As a matter of fact, the sequential addition of methylmag-... 

The method is not restricted to secondary aryl alcohols and very good results were also obtained for secondary diols [39], a- and S-hydroxyalkylphosphonates [40], 2-hydroxyalkyl sulfones [41], allylic alcohols [42], S-halo alcohols [43], aromatic chlorohydrins [44], functionalized y-hydroxy amides [45], 1,2-diarylethanols [46], and primary amines [47]. Recently, the synthetic potential of this method was expanded by application of an air-stable and recyclable racemization catalyst that is applicable to alcohol DKR at room temperature [48]. The catalyst type is not limited to organometallic ruthenium compounds. Recent report indicates that the in situ racemization of amines with thiyl radicals can also be combined with enzymatic acylation of amines [49]. It is clear that, in the future, other types of catalytic racemization processes will be used together with enzymatic processes. 

A priori borataethenes would be expected to be much more stable than the corresponding boraethenes because, as Rundle presciently noted about organometallic structures,50 all low-lying atomic orbitals are involved in the bonding. In fact, the stabilization of 52 is the driving force for the acidity of C—H bonds of proper orientation a to tricoordinate boron. Such acidity was first detected by Rathke and Kow through the treatment of B-methyl-9-borabicyclo[3.3.1] nonane (53) with hindered lithium amides, such as lithium 2,2,6,6-tetramethylpiperidide51 (Eq. 18) ... 

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