Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

Abstract

It was in Saint Petersburg that in 1915, jointly with his coworker Mariya Skanawy-Grigorjewa, he conducted the experiments on reactions of CNMe with platinum complexes and obtained platinum carbene species formed via nucleophilic addition of hydrazine to Pt IIactivated methylisocyanide [Tschugajeff (Chugaev), L.; Skanawy-Grigorjewa, M.

Palladium(0)-Catalyzed Benzylic C(<i>sp</i>³)–H Functionalization for the Concise Synthesis of Heterocycles and Its Applications

“…We initially focused on a cascade reaction involving a combination of benzylic C(sp 3 )-H functionalization with Pd-catalyzed isocyanide insertion [81][82][83][84][85][86] for the synthesis of indole derivatives, which are an important class of nitrogen-containing heterocycles in the pharmaceutical sciences. Several other groups had previously reported concise methods for the synthesis of carbo-and heterocyclic systems through isocyanide insertion and C(sp 2 )-H activation steps.…”

Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

“…These results are accordingly discussed in the sections that follow. In the continuation of our projects focused on metal-mediated reactions of isocyanides [15,[58][59][60][61][62][63][64][65][66][67][68] and on non-covalent interactions [15,58,[69][70][71][72][73][74][75][76][77], we recently reported on the coupling between cis-[PdCl 2 (CNXyl) 2 ] (Xyl = 2,6-Me 2 C 6 H 4 ) and various thiazol-and thiadiazol-2-amines that leads to a mixture of two regioisomeric binuclear diaminocarbene complexes corresponding to kinetically (3a-d) or thermodynamically (4a-d) controlled regioisomers (Scheme 1). There is an equilibrium between these two species in CHCl 3 solutions that depends on the energy difference between two types of intramolecular CBs, viz.…”

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

“…Metal-involving reactions of such versatile substrates as isocyanides attract significant attention, which is collaterally reflected in a large number of reviews and books published in this field [1][2][3][4][5][6][7][8]. Among various metal centers that promote conversion of RNC species, copper(I) plays a remarkable role insofar as this labile metal center provides efficient cyclization of isocyanides to various heterocyclic systems (for recent examples see [9][10][11][12][13][14]).…”

“…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.…”