Lactam cyclic amines from

Sodium tetrahydridoborate I alcohols Cyclic amines from lactams s. 44, 72... 

Pingen D, Vogt D (2014) Amino-alcohol cyclization selective synthesis of lactams and cyclic amines from amino-alcohols. Catal Sci Technol 4(l) 47-52... 

The lactam formation from the oxidation of cyclic amines (353, for example) probably proceeds via intermediate 364. The nitrogen-iodine bond dissociates to give imine 365, which reacts again with a second equivalent of iodosobenzene to give another intermediate 366. Finally, 366 on reductive... 

Early attempts to extend the halolactonization procedure to yield lactams gave cyclic imidates instead, but several approaches favor lactam products. These include working with silyl imidates, imidate esters or oxazolines, using sulfonylcarbamates or other acidic amides or by using hydroxyl-amine derivatives with increased nucleophilicity due to the a-effect. Lactams can also be favored as a consequence of steric requirements. In a few cases, amines can be cyclized to cyclic amines many lead references are given in a recent report on cyclic hydroxylamines such as (64). Veiy recent work has provided a fairly general iodolactamization procedure from unsaturated amides, trimethylsilyl triflate and iodine (Scheme 89). ... 

A fourth type of product, a carbamate RNHCOOR , can be obtained from primary or secondary amines, if these are treated with CO, O2, and an alcohol R OH in the presence of a catalyst. " Primary amines react with dimethyl carbonate in supercritical CO2 (see p. 414) to give a carbamate. " Carbamates can also be obtained from nitroso compounds, by treatment with CO, R OH, Pd(OAc)2, and Cu(OAc)2, " and from nitro compounds. " When allylic amines (R2C=CHRCHRNR 2) are treated with CO and a palladium-phosphine catalyst, the CO inserts to produce the p,y-unsa-turated amides (R2C=CHRCHRCONR 2) in good yields. " Ring-expanded lactams are obtained from cyclic amines via a similar reaction (see also, 16-22). Silyloxy carbamates (RNHC02SiR 3) can be prepared by the reaction of a primary amine with carbon dioxide and triethylamine, followed by reaction with triisopropylsilyl triflate and tetrabutylammonium fluoride. ... 

In macroscale electrolyses, lactams or fully saturated cyclic amines are obtained in good yields from imides in strongly acidic electrolytes [1-5] for example, 7V-methylsucci-nimide is reduced in good yield to A -methylpyrrolidone at a lead cathode in sulfuric acid solution [140]. 

Lactams from cyclic amines. A mixture of iodosobenzene and water stirred for 15 min, the slurry cooled to 0°, treated in one portion with pyrrolidine, stirred at 9" for 1 h, then at room temp, until a clear soln. was obtained (4-5 h) - 2-pyrrolidinone. Y 49%. F.e. inch 3,4-dihydroisocarbostyrils and 2-piperidones, also nitriles from prim, amines, and cyclic ketones from cycloalkylamines, s. R.M. Moriarty et al., Tetrahedron Letters 29, 6913-6 (1988) cyclic azomethines in methylene chloride cf. ibid. 6917-20. 

Schiff bases s. Azomethines Schlotterbeck s. Buchner Schmidt reaction 17, 524 —, amines from carboxylic acids 19, 305 20, 366 —, lactams from ketones, cyclic, ring expansion... 

Alternatively, if an aldehyde was formed from MFO metabohsm of the cyclic amine it may undergo direct oxidation catalyzed by aldehyde dehydrogenase to form a carboxylic acid. The acid can then condense with the amine to again form a lactam. 

The cyclic carbonate of benzoin (4,5-diphenyl-l,3-dioxol-2-one, prepared from benzoin and phosgene) blocks both hydrogen atoms of primary amines after dehydration acid stable, easily crystallizable Sheehan oxazolinones are formed, which are also called Ox derivatives. The amine is quantitatively deblocked by catalytic hydrogenation in the presence of 1 equiv. of aqueous acid (J.C Sheehan, 1972, 1973 M.J. Miller, 1983). An intelligent application to syntheses of acid labile -lactams is given in the previous section (p. 161). 

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