6533b829fe1ef96bd128998b
RESEARCH PRODUCT
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
Saad TouqeerLaura IeloCristina PrandiWolfgang HolzerAlexander RollerLaura CastoldiJessica LombinoVittorio PaceVittorio Pacesubject
Trifluoromethyl010405 organic chemistryIminemetalationGeneral Chemistrycarbenoids; chemoselectivity; homologation; imines; metalation010402 general chemistry01 natural sciencesCombinatorial chemistryCatalysis0104 chemical sciencesCatalysisβ diketiminatechemistry.chemical_compoundDual rolechemistrychemoselectivityiminesHalogenNucleophilic substitutionhomologationcarbenoidsCarbenoiddescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2020-09-09 | Angewandte Chemie International Edition |