Access to the Cinnoline Scaffold via Rhodium-Catalyzed Intermolecular Cyclization under Mild Conditions
Chao Song1, Chen Yang1, Feifei Zhang1
1Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Chemistry for Life Sciences, Nanjing University , Nanjing 210093, China.
Abstract:
Herein, we report Rh(III)-catalyzed, N-amino (hydrazine)-directed C-H functionalization with α-diazo-β-ketoesters for access to the cinnoline scaffold. A diverse set of nondiscriminating conditions obtained for a highly efficient test transformation prompted use of a substrate-replacement technique for an in-depth search of experimental parameter space and pinpointing of the optimized conditions. A successive C-H activation/C-C coupling/intramolecular dehydration mechanistic sequence is proposed. The ability to perform gram-scale synthesis proves the synthetic utility of this simple, yet efficient, method.
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