Halogen-Imparted Reactivity in Lithium Carbenoid Mediated Homologations of Imine Surrogates: Direct Assembly of bis-Trifluoromethyl-β-Diketiminates and the Dual Role of LiCH2I
Laura Ielo
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorLaura Castoldi
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorSaad Touqeer
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorJessica Lombino
Fondazione Ri.MED, Via Bandiera 11, 90133 Palermo, Italy
University of Palermo, Department STEBICEF, Via Archirafi 32, 90123 Palermo, Italy
Search for more papers by this authorAlexander Roller
University of Vienna, X-Ray Structure Analysis Center, Waehringerstrasse 42, 1090 Vienna, Austria
Search for more papers by this authorCristina Prandi
University of Turin, Department of Chemistry, Via P. Giuria 7, 10125 Turin, Italy
Search for more papers by this authorWolfgang Holzer
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorCorresponding Author
Vittorio Pace
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
University of Turin, Department of Chemistry, Via P. Giuria 7, 10125 Turin, Italy
Search for more papers by this authorLaura Ielo
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorLaura Castoldi
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorSaad Touqeer
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorJessica Lombino
Fondazione Ri.MED, Via Bandiera 11, 90133 Palermo, Italy
University of Palermo, Department STEBICEF, Via Archirafi 32, 90123 Palermo, Italy
Search for more papers by this authorAlexander Roller
University of Vienna, X-Ray Structure Analysis Center, Waehringerstrasse 42, 1090 Vienna, Austria
Search for more papers by this authorCristina Prandi
University of Turin, Department of Chemistry, Via P. Giuria 7, 10125 Turin, Italy
Search for more papers by this authorWolfgang Holzer
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
Search for more papers by this authorCorresponding Author
Vittorio Pace
University of Vienna, Department of Pharmaceutical Chemistry, Althanstrasse 14, 1090 Vienna, Austria
University of Turin, Department of Chemistry, Via P. Giuria 7, 10125 Turin, Italy
Search for more papers by this authorDedicated to Professor José Vicente Sinisterra on the occasion of his 70th birthday
Abstract
The selective formal insertion (homologation) of a carbon unit bridging the two trifluoroacetamidoyl chlorides (TFAICs) units is reported. The tactic is levered on a highly chemoselective homologation–metalation–acyl nucleophilic substitution sequence which precisely enables to assemble novel trifluoromethylated β-diketiminates within a single synthetic operation. Unlike previous homologations conducted with LiCH2Cl furnishing aziridines, herein we exploit the unique capability of iodomethyllithium to act contemporaneously as a C1 source (homologating effect) and metalating agent. The mechanistic rationale grounded on experimental evidences supports the hypothesized proposal and, the structural analysis gathers key aspects of this class of valuable ligands in catalysis.
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