Synthesis of α-, ß-, and γ-Carbolines via Intramolecular Cyclization of Azidomethyl(indolyl)acrylates Involving PIFA-BF3·OEt2/DBU-Mediated Cyclization as well as Thermolysis Approaches.

In this study, we present our findings on the synthesis of α-, ß-, γ-carbolines via PIFA/BF3·OEt2-mediated intramolecular cyclization of isomeric azidomethyl(indolyl)acrylates. Alternately, 1,5,7-triazabicyclo[4.4.0]dec-5-ene/1,8-diazabicyclo(5.4.0)undec-7-ene (TBD/DBU)-mediated Michael addition followed by intramolecular cyclization of isomeric 2/3-(azidomethyl)indol-3/2-yl)acrylates also furnished the respective ß- and γ-carboline derivatives. Unexpectedly, the thermolysis of 2-(azidomethyl)-3-(indol-3-yl)acrylates led to the formation of ethyl 5-(2-(phenylsulfonamido)aryl)nicotinates along with γ-carbolines, via nitrene insertion followed by rearrangement and cyclization. The isomeric 2-(azidomethyl)-3-(indol-2-yl)acrylate upon thermolysis led to the expected δ-carboline. Thermal intramolecular nitrene insertion reaction could also be extended for accessing pyrido benzothiophene, pyrido thiophene, and quinoline.

A Formal (4 + 2) Cycloaddition of Phosphorus Ylides: Synthesis of Aromatic and Heteroaromatic 1,2-Diesters and Diones.

Heteroarylmethylenephosphorus ylides underwent Michael addition with alkynediones and alkynediesters, followed by intramolecular cyclization and elimination of triphenylphosphine oxide to afford 1,2-diaroylbenzenes and 1,2-alkoxycarbonylcarbo- and heterocycles. The analogous (4 + 2) cycloaddition led to the formation of 2,3-diaroylquinolines.