Benzoazepinone

The Heck-type cyclization in the presence of Pd(OAc)2/PPh3 catalyst and silver carbonate base leads to good to excellent yields of the corresponding thieno benzoazepinones 12d and 14d (see Equations (1) and (2), Section 2.1.1.1 (2005TL8177)). 

Two products (54 and 55) are formed in 63 and 23% yields, respectively, when 3-ethoxyisoindolenone is irradiated with isobutylene in methylene chloride solvent at —12 °C. The major product (54) has been identified as the product of a photochemical ene type reaction, and the cycloadduct structure 55 has been assigned to the minor photoproduct. Cycloadduct and ene type products (56 and 57) are also formed in 25 and 23% yields, respectively, when 50 is irradiated in the presence of tetramethylethylene. Additionally an unprecedented benzoazepinone (58) is formed in 12% yield. 

Using the same procedure as for the synthesis of the related five- and six-membered benzolactams, the benzoazepinone derivatives (27) have been synthesized in good yield. This palladium-catalyzed procedure has more recently been extended to the synthesis of a number of antibiotics. A key step in the synthesis of anthramycin, for example, is the palladium-catalyzed insertion of CO into the amine (28). ... 

Santos, L.S. and Pilli, R.A. (2002) The intramolecular Heck reaction and the synthesis of indolizidinone, quinolizidinone and benzoazepinone derivatives. Synthesis, 87-93. 

In 2012, a palladium-catalyzed ring opening of aminocyclopropyl Ugi adducts was presented. Dihydropyridine and benzoazepinone derivatives were produced in moderate yields (Scheme 3.35a). Catellani and co-workers reported a palladium-catalyzed synthesis of substituted phenanthridine derivatives in 2008. Selectively substituted phenanthridine derivatives were obtained by a facile reaction of o-allqrlated aiyl iodides, o-bromoar-enesulfonylanilines and activated olefins in the presence of palladium and norbornene as catalysts. The reaction takes place under mild conditions to give the products in satisfactory yields using readily available starting materials (Scheme 3.35b). 

Generation of the allenes 360 in situ affords the benzoazepinones 361 in good yields via intramolecular cycloadditions... 

---