Imides from unsaturated amides

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). ... 

C for 6 h afforded the alkylated imides in 60-84% yields. The last approach was extended to unsaturated carboxylic amides. The diene 0,N-acetal 86 was prepared from the amide 85 in high yields and subsequently treated with azoinitiator V-70 to afford the desired products (Scheme 13). ... 

A few diamides have been converted to diamines. For the most part, the conversion of unsaturated amides is unsatisfactory however, a-allylphenylacetamide is transformed to a-allylbenzylamine in a 90% yield. Aromatic amides having free or methylated phenolic groups are treated preferably with sodium hypochlorite rather than hypobromite in order to avoid excessive ring halogenation. Certain amino acids like anthranilic acid and /3-alanine have been synthesized from the appropriate imides. ... 

A series of cross-linkable copoly(amide—imides) is known to be possible from aromatic diamines and substituted isophthaloyl chlorides containing unsaturated imide rings as a pendent function (13). 

The chemistry of imidates and their methods of synthesis have been reviewed [32], Imidates are mainly available via the Pinner synthesis, via iminochlorides, from amides, from aldehydes and ketones, and via unsaturated systems [32]. 

Cyclic sulfonamides are Lermed sultams. From the enantiomeric 10-camphorsulfonic acids, both enantiomers of camphorsultam (49) are readily available by reduction of the intermediate sulfon-imide 484fi 50 and are commercially available. They have been used for the formation of amides with unsaturated acids, which are useful chiral dienophiles and dipolarophiles (Sections D. 1.6,1.1.1- and D. 1.6.1.2.1.) or undergo osmium tetroxide catalyzed dihydroxylations (Section D.4.4.). Other amides may be used for enolate reactions (Sections D.1.1.1.3.1., D.l.5.2.1. and D.4.3.). The. V-fluorinated derivative was obtained by direct fluorination of the sultam with 10% fluorine in nitrogen at low temperature5 , and has been used for the enantioselective formation of C —F bonds (Section D.3.). 

Radical substitution of the hydrogen from the methyl groups PHj OH,X Kl( -HY CH3 X CH, hc=ch X-Y = Br-Br,C1-C1 (12) RS0.-C1 (13) I 1 ( ) Halogenation, sulfonation, binding of maleric anhydride group, unsaturated carboxyl acids, amides, imides, esters, epoxides, amines, alcohol can be used Product of (12) is precursor for PCMs, that of (13) for direct PCMs. 

---