A one-pot cycloaddition strategy for obtaining γ-carbolines under mild conditions was developed. The reaction represents a new approach to the annulation of a pyridine ring to an indole core. Treating 2-methyl-3-benzoylindoles with lithium diisopropyl amide leads to the elimination of a proton from the 2-methyl group. The organolithium compounds generated were found to react with nitriles. The resulting 4,5-dihydro-1H-pyrido­[4,3-b]­indol-1-ols undergo spontaneous water elimination to give the corresponding γ-carbolines. The applicability of this reaction for the synthesis of isoquinolines has been shown. For the first time, a lithium atom was found to be part of an eight-centered polycyclic transition state according to a detailed DFT PCM/DFT/B3LYP/6-311++G­(d,p) and ab initio PCM/MP2//HF/6-311++G­(d,p) quantum chemical study.

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A new approach for the annulation of a thiopyrane ring to an indole core under mild conditions was developed. Treating 2-methyl-3-acylindoles with lithium diisopropyl amide leads to the elimination of a proton from the 2-methyl group. The lithium indole-2,3-dienolates obtained were found to react with CS2 to give the corresponding thiopyrano­[4,3-b]­indole-3­(5H)-thiones. The mechanism represents a stepwise addition through ion-pair formation, according to PCM/B3LYP/6-311++G**, PBE1PBE/6-311++G**, and MP2//HF/6-311++G** quantum chemical calculations. AIM calculations revealed the essential role of the Li atom at all stages of the process.

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