5221-67-0Relevant articles and documents
Oxidative Access via Aqua Regia to an Electrophilic, Mesoionic Dicobaltoceniumyltriazolylidene Gold(III) Catalyst
Vanicek, Stefan,Beerhues, Julia,Bens, Tobias,Levchenko, Volodymyr,Wurst, Klaus,Bildstein, Benno,Tilset, Mats,Sarkar, Biprajit
, p. 4383 - 4386 (2019)
A gold(III) complex with the hitherto most electron poor mesoionic carbene ligand is presented. Aqua regia was the oxidizing agent of choice for the synthesis of this unusual organometallic compound. The AuIII complex is redox-rich and also act
Heterogenized gold(I)-carbene as a single-site catalyst in continuous flow
Lothschuetz, Christian,Szlachetko, Jakub,Van Bokhoven, Jeroen A.
, p. 443 - 448 (2014)
Catalytically active gold(I)-carbene complexes on a polystyrene backbone were synthesized by treating metal-coordinated isocyanides with the nitrogen nucleophile of a piperazine group bonded to the polystyrene. The local environment of the metal was readi
Synthesis and Catalytic Activity of Atrane-type Hard and Soft Lewis Superacids with a Silyl, Germyl, or Stannyl Cationic Center
Tanaka, Daiki,Konishi, Akihito,Yasuda, Makoto
supporting information, p. 3118 - 3123 (2021/09/08)
The synthesis and isolation of atrane-type molecules 1E+ (E=Si, Ge, or Sn) having a cationic group 14 elemental center are reported. The cations 1E+ act as hard and soft Lewis superacids, which readily interact with various hard and soft Lewis basic substrates. The rigid atrane framework stabilizes the localized positive charge on the elemental center and assists the formation of the well-defined highly coordinated states of 1E+. The cations were applied to the hydrodefluorination, Friedel-Crafts reaction, alkyne cyclization, and carbonyl reduction as Lewis acid catalysts. Most notably, [1Si][ClO4] exhibits unique chemoselectivity that depends on a solvent in the competitive reaction of silyl enol ether with a mixture of benzaldehyde dimethyl acetal and benzaldehyde. Our findings indicate the potential of hard and soft Lewis superacids in organic synthesis.
Silver-Free Au(I) Catalysis Enabled by Bifunctional Urea- and Squaramide-Phosphine Ligands via H-Bonding
Echavarren, Antonio M.,Franchino, Allegra,Martí, àlex,Nejrotti, Stefano
, p. 11989 - 11996 (2021/07/06)
A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N-propargyl benzamides, as well as in a 1,6-enyne cycloisomerization, a tandem cyclization-indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H-bond donor via an associative mechanism, and the subsequent cyclization step.