The CF 3 Group as a Synthon of the CF + Unit in Palladium Chemistry.

Autor: Joven-Sancho D; Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, Zaragoza, 50009, Spain., Baya M; Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, Zaragoza, 50009, Spain., Martín A; Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, Zaragoza, 50009, Spain., Orduna J; Instituto de Nanociencia y Materiales de Aragón (INMA), CSIC-Universidad de Zaragoza, Zaragoza, 50009, Spain., Menjón B; Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, Zaragoza, 50009, Spain.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jun 21; Vol. 63 (26), pp. e202403108. Date of Electronic Publication: 2024 May 08.
DOI: 10.1002/anie.202403108
Abstrakt: The homoleptic trifluoromethyl-palladium(II) complex [Pd(CF 3 ) 4 ] 2- (1) is shown to be highly active towards amines. Thus, when treated with primary amines RNH 2 , it readily undergoes aminolysis of one of the CF 3 ligands affording the isocyanide complexes [(CF 3 ) 3 Pd(CNR)] - (R=aryl). In this process the original CF 3 group undergoes total defluorination. Interestingly, the reaction of 1 with secondary amines R 2 NH proceeds with loss of just two F-substituents, whereby the Fischer-type fluoroaminocarbene complexes [(CF 3 ) 3 Pd(CFNR 2 )] - are formed (R=Et, Ph). The reaction of 1 with diamines affords different [(CF 3 ) 3 Pd(NHC)] - complexes containing sterically non-demanding NHC ligands. Representative examples of various topologies are reported based on the common imidazolidin-2-ylidene or benzimidazolin-2-ylidene rings as well as the expanded-ring perimidin-2-ylidene. This metal-tailored synthetic route, where a CF 3 group acts as a pre-carbenic unit, is unprecedented in the vast NHC-chemistry. It takes place under very mild conditions and is envisaged to be extensible to other non-isolable NHC ligands. The key difluorocarbene intermediate [(CF 3 ) 3 Pd(CF 2 )] - is experimentally detected.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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