937807-95-9Relevant academic research and scientific papers
Lowering the barrier to C?H activation at IRIII through pincer ligand design
Chu, Wan-Yi,Goldberg, Karen I.,Rubashkin, Sophie B.
supporting information, p. 1296 - 1302 (2021/05/29)
Selective C?H activation of benzene and n-octane under mild conditions by a pincer IrIII carboxylate complex, (CCCMesityl)Ir(OAc)2(OH2) (1a), is described. A kinetic study of benzene activation was undertaken, and the resulting Eyring analysis informed the design of a tButylCCCMethyl-ligated IrIII carboxylate, which exhibited a ΔG? value for the reaction lower than that observed for 1a. Elimination of the aquo ligand was found to further lower the ΔG? value of benzene activation, enabling C?H activation by IrIII at temperatures as low as 30 °C.
Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
Roscales, Silvia,Csák?, Aurelio G.
, p. 1667 - 1671 (2018/03/23)
The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.
Monoanionic bis(carbene) pincer complexes featuring cobalt(I-III) oxidation states
Ibrahim, Abdulrahman D.,Tokmic, Kenan,Brennan, Marshall R.,Kim, Dongyoung,Matson, Ellen M.,Nilges, Mark J.,Bertke, Jeffery A.,Fout, Alison R.
supporting information, p. 9805 - 9811 (2016/07/06)
The synthesis and characterization of a series of cobalt complexes featuring a pincer bis(carbene) ligand of the meta-phenylene-bridged bis-N-heterocyclic carbene (ArCCC, Ar = 2,6-diispropylphenyl or mesityl) are reported. Cleavage of the aryl C-H bond of the ligand was achieved in a one-pot metalation procedure using Co(N(SiMe3)2)2(py)2, an equivalent of exogenous base, and trityl chloride to form the (DIPPCCC)CoCl2py complex. This species could be reduced to the Co(ii) and Co(i)-N2 molecules with the appropriate equivalents of reductant. Subsequent generation of (MesCCC)CoI-III derivatives with the mesityl ligand proceeded in good yields. A suite of characterization techniques and the interconversion between all three oxidation states of the cobalt complexes is described.
Iridium complexes of CCC-pincer N-heterocyclic carbene ligands: Synthesis and catalytic C-H functionalization
Chianese, Anthony R.,Mo, Allen,Lampland, Nicole L.,Swartz, Raymond L.,Bremer, Paul T.
scheme or table, p. 3019 - 3026 (2010/10/03)
A series of four meta-phenylene-bridged bis-benzimidazolium chlorides were synthesized as precursors to rigid, monoanionic, CCC-pincer N-heterocyclic carbene ligands. For ligands with mesityl, 3,5-xylyl, or 3,5-di-tert-butylphenyl side groups, reaction with [Ir(1,5-cyclooctadiene)Cl]2 in acetonitrile with either excess triethylamine or stoichiometric cesium fluoride as base gave neutral, iridium(III) pincer complexes of the formula Ir(CCC)HCl(MeCN), which were purified by chromatography on silica gel. Metalation failed under these conditions for a 2,6-diisopropylphenyl-substituted derivative. In combination with NaOtBu, these complexes form active catalysts for the acceptorless dehydrogenation of cyclooctane and for arene C-H borylation in neat arene solvent.
Reactive 4a-alkyl-4aH-carbazoles by catalytic dearomatisation, and their unusual dimerisation and dealkylation reactions
Bedford, Robin B.,Butts, Craig P.,Haddow, Mairi F.,Osborne, Robert,Sankey, Rosalind F.
supporting information; experimental part, p. 4832 - 4834 (2009/12/08)
Despite their intrinsic instability, 4a-alkyl-4aH-carbazoles can be generated by a catalytic dearomatisation process; their reactivity is demonstrated by facile dealkylation and highly unusual cyclodimerisation processes.
Novel benzo-and pyrido-anellated 1, 3-azaphospholes
Heinicke,Aluri,Adam,Jones
body text, p. 779 - 782 (2009/04/04)
We present the synthesis of OH-functional and bulky N-substituted benzazaphospholes, novel pyrido-azaphospholes, addition versus CH-metalation by tBuLi and reactions with electrophiles yielding a novel asymmetric P,N-heterocyclic ethylene-1,2-bis(phosphin
Highly stereoselective formal [3 + 3] cycloaddition of enals and azomethine imines catalyzed by N-heterocyclic carbenes
Chan, Audrey,Scheidt, Karl A.
, p. 5334 - 5335 (2008/02/04)
N-Heterocyclic carbenes derived from N-mesityl benzimidazolium salts are effective catalysts for generating homoenolate species from α,β-unsaturated aldehydes. The nucleophilic intermediate adds to azomethine imines, and the resulting activated carbonyl u
