Novel Palladium–Aminocarbene Species Derived from Metal-Mediated Coupling of Isonitriles and 1,3-Diiminoisoindoline: Synthesis and Catalytic Application in Suzuki–Miyaura Cross-Coupling

Abstract

The reaction between metal-bound isonitriles in cis-[PdCl 2 (CNR 1 ) 2 ] [R 1 = cyclohexyl (Cy) 1, Bu t 2, C 6 H 4 (2,6-Me 2 ) (Xyl) 3, CMe 2 CH 2 CMe 3 4] and 1,3-diiminoisoindoline (9) in CHCl 3 under reflux for 4 h provides the carbene species [Pd{C(NC a (C 6 H 4 CNHN b ))N(H)R 1 } 2 ] a−b (R 1 = Cy 10, 82% isolated yield) or cis-[PdCl{C(NC a (C 6 H 4 CNHN b )) N(H)R 1 }(CNR 1 )] a−b (R 1 = Bu t 11, 78%; Xyl 12, 84%

Application of palladium complexes bearing acyclic amino(hydrazido)carbene ligands as catalysts for copper-free Sonogashira cross-coupling

“…The crystallographic data and processing parameters for 38 are listed in (2.001(3) Å) [27], and cis-[PdCl{C(N@ C(C 6 H 4 CNHN))@N(H)Xyl}(CNXyl)] (2.015(9) Å) [28]. In 38, the carbene moiety is roughly planar and the angles around the carbene C1 atoms range from 113.1°to 129.3°therefore sustaining the sp 2 hybridization of this atom.…”

Characterization of Cu-ligand bonds in tris-pyrazolylmethane isocyanide copper(I) complexes based upon combined X-ray diffraction and theoretical study

“…In the framework of our project on reactions of metal-activated isocyanide species (for review see [8], for recent works see [38,[41][42][43][44][45][46][47][48]), we recently synthesized a series of [CuBr(CNR) 3 ] complexes and, after an X-ray structural study combined with theoretical calculations, we verified specific structural features of [CuBr (CNR) 3 ]; the results of the AIM, NBO, and CDA analyses indicate that the Cu-C coordination bonds are determined mainly by electrostatics. In this work, we consider another case of RNC ligation to a Cu I center, when coordination environment of the complex featuring three relatively good r-donor ligands and only one isocyanide as moderate r-donor and p-acceptor.…”

New acyclic Pd–diaminocarbene catalyst for Suzuki arylation of meso-chlorosubstituted tricarboindocyanine dyes

“…1 The catalytic activity of Pd-complexes with acyclic diaminocarbenes (ADCs) in the corresponding reactions 2 has been recently proved, surpassing in some cases the activity of NHC-based catalysts. 3 These catalysts have became even more attractive, since a simple procedure for their preparation has been developed, which consists of the addition of nitrogen nucleophiles (benzophenone hydrazone, 3 1,3-diiminoisoindolin-1-one, 4 3-iminoisoindolin-1-one, 5 and aniline 6 ) to palladium-coordinated isonitriles.…”