Function of a new N-heterocyclic carbene ligand based on the concept of a chiral mimetic is described. With (4R,5R)-4,5-diphenyl-1,3-dialkyl-4,5-dihydro-3H-imidazol-1-ium tetrafluoroborates as N-heterocyclic carbene precursors, Rh-catalyzed enantioselective arylation (up to 27% ee) of aromatic aldehydes with arylboronic acids and Pd-catalyzed enantioselective intramolecular alpha-arylation (up to 66% ee) of N-(2-bromoaryl)-N-alkyl-2-arylpropanamides are investigated.
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http://dx.doi.org/10.1248/cpb.54.1576 | DOI Listing |
Chem Asian J
December 2024
CSIR - North East Institute of Science and Technology, Materials Sciences and Technology Division, Pulibor, CSIR-NEIST, 785006, Jorhat, INDIA.
Bimetallic catalysts have gained attention as promising contenders, owing to the synergistic interaction between two distinct metal centers. In this study, we present two N-heterocyclic carbene iridium(III) pentamethylcyclopentadienyl complexes [Cp*Ir(fcpyNHC)Cl]PF6 (1) and [Cp*Ir(pyNHC)Cl]PF6 (2) where 1 includes a ferrocene moiety acting as a bimetallic complex. Using ceric ammonium nitrate as a sacrificial oxidant, both complexes were tested for water oxidation.
View Article and Find Full Text PDFJ Org Chem
December 2024
College of New Energy, State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, P. R. China.
The photocatalytic dearomative 1,4-hydroboration of naphthalenes with an N-heterocyclic carbene borane (NHC-BH) complex was reported herein with controllable regioselectivity and chemoselectivity. This protocol yielded a wide range of naphthalene derivatives bearing various functional groups, notably bioactive compounds. Hydroboration occurred through the cooperation of photoredox and hydrogen atom transfer via boryl radical addition to naphthalene and further selective protonation.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Pharmaceutical Science, Hengyang Medical School, University of South China, Hengyang 421001, Hunan, China.
Although the radical hydroboration of alkenes with N-heterocyclic carbene (NHC) borane is well documented, the radical hydroboration of alkynes, especially terminal alkynes, remains challenging. Herein, a photoredox-catalyzed radical -hydroboration of alkynes with NHC borane has been developed, which provided various alkenyl boron compounds in moderate to good yields. This protocol exhibits a broad substrate scope, as both internal and terminal alkynes were compatible.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants.
View Article and Find Full Text PDFInorg Chem
December 2024
Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 19, 30100 Murcia, Spain.
Dicationic, -symmetrical, tris-chelate Pt(IV) complexes of general formula [Pt(trz)(N∧N)](OTf), bearing two cyclometalated 4-butyl-3-methyl-1-phenyl-1-1,2,3-triazol-5-ylidene (trz) ligands and one aromatic diimine [N∧N = 2,2'-bipyridine (bpy, ), 4,4'-di--butyl-2,2'-bipyridine (dbbpy, ), 4,4'-dimethoxi-2,2'-bipyridine (dMeO-bpy, ), 1,10-phenanthroline (phen, ), 4,7-diphenyl-1,10-phenanthroline (bphen, ), dipyrido[3,2-:2',3'-]phenazine (dppz, ), or 2,3-diphenylpyrazino[2,3-][1,10]phenanthroline (dpprzphen, )] are obtained through chloride abstraction from [PtCl(trz)] () using AgOTf in the presence of the corresponding diimine. Complexes show long-lived phosphorescence from LC excited states involving the diimine ligand, with quantum yields that reach 0.18 in solution and 0.
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