Alcoholysis of amides

Amides. Alcoholysis of amides provides another method for synthesizing esters ... 

Alcoholysis of amides is possible but is seldom performed,678 except for the imidazolide type of amide (101). 

Alcoholysis of amides was first reported for the preparation of alkaline alkoxides. The reaction was carried out in liquid ammonia solutions and was aimed at the obtaining of the derivatives of aromatic alcohols ... 

Alcoholysis of amides is possible, although it is usually difficult. It has been most common with the imidazolide type of amides (e.g., 100). For other amides, an activating agent is usually necessary before the alcohol will replace the NR2 unit. Dimethylformamide, however, reacted with primary alcohols in the presence of 2,4,6-trichloro-l,3,5-pyrazine (cyanuric acid) to give the corresponding formate ester. Treatment of an amide with triflic anhydride (CF3SO2OSO2CF3) in the... 

O hIb r CXnR2 Aminolysis of oxygen esters, alcoholysis of amides. 

Acid chloride, alcohols from, 804 alcoholysis of, 802-803 amides from, 803-804 amines from, 933-935 amjnolysis of, 803-804 carboxylic acids from, 802 electrostatic potential map of, 791... 

Lipases are generally inactive on the amide bond. One notable exception is the hydrolysis and alcoholysis of P-lactams by CAL-B [108-112]. For example, CAL-B... 

In a similar way to the aminolysis of the P-N bond mentioned above (Scheme 9), alcoholysis of phosphinous amides leads to the alkyl esters of the respective phosphinous acids [30, 121]. This reaction occurs with inversion of the absolute configuration of the phosphorus atom, and has been used in a synthetic sequence leading to optically active tertiary phosphanes 22 [122] (Scheme 23). 

The zinc complex of a tripodal N2S20 pentadentate ligand undergoes amide alcoholysis of a coordinated amide group.893 Examples of amide hydrolysis are known for other ligand systems.894... 

Earlier work in this field has been thoroughly reviewed [1,2]. However, to illustrate in a sensible and logical way the evolution from simple metal ion promotion of acyl transfer in supramolecular complexes to supramolecular catalysts capable of turnover catalysis, an account of earlier work is appropriate. The following sections present a brief overview of our earlier observations related to the influence of alkaline-earth metal ions and their complexes with crown ethers on the alcoholysis of esters and of activated amides under basic conditions. 

Indeed the alcoholysis of metal amides is an excellent method for the synthesis of alkoxides. However, some synthetic utility to this reaction has been found for the synthesis of aminoboranes where the equilibrium can be forced to the right by using either an involatile or a chelating amine.59,60 Hydrocarbon solutions of Mo2Me2(OBu )4 also react with MeNHCH2CH2NHMe (>6 equiv.) to give Mo2(MeNCH2CH2NMe)3 with the liberation of methane (2 equiv.) and /-butyl alcohol.61... 

A series of very volatile alkaline-earth compounds with pendent ether groups, [M(OC-/-Bu(CH2OR)2)2]2 (M = Ca, Sr, Ba R = i-Pr or Et), have been synthesized by the halide metathesis and metal/ammonia methods as well as by reaction between the metal amides M(N(SiMe3)2)2(THF) and the alcohols HOC-t-Bu(CH2OR)2.48 Alcoholysis of metal amides has... 

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