Halogen-Imparted Reactivity in Lithium Carbenoid Mediated Homologations of Imine Surrogates: Direct Assembly of bis-Trifluoromethyl-β-Diketiminates and the Dual Role of LiCH 2 I

Halogen-Imparted Reactivity in Lithium Carbenoid Mediated Homologations of Imine Surrogates: Direct Assembly of bis-Trifluoromethyl-β-Diketiminates and the Dual Role of LiCH 2 I

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 triflu...

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Veröffentlicht in:Angewandte Chemie International Edition 2020-11, Vol.59 (47), p.20852-20857
Hauptverfasser: Ielo, Laura, Castoldi, Laura, Touqeer, Saad, Lombino, Jessica, Roller, Alexander, Prandi, Cristina, Holzer, Wolfgang, Pace, Vittorio
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container_issue 47
container_start_page 20852
container_title Angewandte Chemie International Edition
container_volume 59
creator Ielo, Laura
Castoldi, Laura
Touqeer, Saad
Lombino, Jessica
Roller, Alexander
Prandi, Cristina
Holzer, Wolfgang
Pace, Vittorio
description 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 LiCH Cl 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.
doi_str_mv 10.1002/anie.202007954
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title Halogen-Imparted Reactivity in Lithium Carbenoid Mediated Homologations of Imine Surrogates: Direct Assembly of bis-Trifluoromethyl-β-Diketiminates and the Dual Role of LiCH 2 I
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