Amides, phthalimides substrates

In general, amino-containing compounds are poor partners in CM due to their tendency to coordinate to the metal catalyst, even when late-transition metal systems are employed. To preserve catalyst activity, amino groups are therefore typically masked as cyanides, carbamates, amides, or phthalimides. In substrates where iV-coordination to the catalyst is less favored, such as with hindered /V-aryl-/V-allylamines, no protecting group is required. 

The use of secondary amides as nucleophiles has been also documented by Mori et al.f Synthesis of imides by this method is not always satisfactory, but phthalimides are prepared in high yield (Scheme 44). An interesting modification of this method consists of the double carbonylation of o-aryl diiodides and proceeds via an initial intermole-cular amidation, followed by the intramolecular one described by Mori (Scheme 45). ° The formation of seven-membered rings was demonstrated by the synthesis of diazepam and a number of anthramycin alkaloids, including Prothracarcin and Tomaymycin (Scheme 46). As mentioned above, for seven-membered rings direct amination is observed as a side reaction. Secondary ureas are also substrates for this reaction, yielding seven-membered cyclic ureas. ... 

In 2011, an efficient approach for the formation of phthalimides through the oxidative carbonylation of aromatic amides was developed by Rovis and coworkers in the presence of rhodium catalyst [9]. In this context, 16 examples were synthesized (Table 15.4). Different kinds of Af-protecting groups such as alkyl (methyl, -butyl, -hexyl, and isopropyl), benzyl, phenyl ethyl, and CHjCOjMe can be utilized with moderate to good efficiency. Substrates bearing para or meta electron-donating groups with the example of methyl, methoxy, and phenyl... 

Photoadditons and Photocyclizations of Phthalimides with a-Silyl-ether, -Thioether, -Amine, and -Amide Substrates... 

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