942-92-7Relevant articles and documents
Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel-Crafts reaction of benzene
Goettmann, Frederic,Fischer, Anna,Antonietti, Markus,Thomas, Arne
, p. 4467 - 4471 (2006)
(Figure Presented) In the footsteps of Liebig and Berzelius: A material first synthesized in 1834, carbon nitride (C3N4), was synthesized in a graphitic mesoporous form by using silica nanoparticles as templates. The resulting electron-rich solid is an active catalyst for the Friedel-Crafts acylation of benzene with hexanoyl chloride. Presumably the catalysis arises from a shift of electron density from the MOs of the catalyst to the unoccupied orbitals of benzene (see picture).
A Proton-Responsive Pyridyl(benzamide)-Functionalized NHC Ligand on Ir Complex for Alkylation of Ketones and Secondary Alcohols
Kaur, Mandeep,U Din Reshi, Noor,Patra, Kamaless,Bhattacherya, Arindom,Kunnikuruvan, Sooraj,Bera, Jitendra K.
supporting information, p. 10737 - 10748 (2021/06/15)
A Cp*Ir(III) complex (1) of a newly designed ligand L1 featuring a proton-responsive pyridyl(benzamide) appended on N-heterocyclic carbene (NHC) has been synthesized. The molecular structure of 1 reveals a dearomatized form of the ligand. The protonation of 1 with HBF4 in tetrahydrofuran gives the corresponding aromatized complex [Cp*Ir(L1H)Cl]BF4 (2). Both compounds are characterized spectroscopically and by X-ray crystallography. The protonation of 1 with acid is examined by 1H NMR and UV-vis spectra. The proton-responsive character of 1 is exploited for catalyzing α-alkylation of ketones and β-alkylation of secondary alcohols using primary alcohols as alkylating agents through hydrogen-borrowing methodology. Compound 1 is an effective catalyst for these reactions and exhibits a superior activity in comparison to a structurally similar iridium complex [Cp*Ir(L2)Cl]PF6 (3) lacking a proton-responsive pendant amide moiety. The catalytic alkylation is characterized by a wide substrate scope, low catalyst and base loadings, and a short reaction time. The catalytic efficacy of 1 is also demonstrated for the syntheses of quinoline and lactone derivatives via acceptorless dehydrogenation, and selective alkylation of two steroids, pregnenolone and testosterone. Detailed mechanistic investigations and DFT calculations substantiate the role of the proton-responsive ligand in the hydrogen-borrowing process.
Nickel-Mediated Photoreductive Cross Coupling of Carboxylic Acid Derivatives for Ketone Synthesis**
Brauer, Jan,Quraishi, Elisabeth,Kammer, Lisa Marie,Opatz, Till
, p. 18168 - 18174 (2021/11/30)
A simple visible light photochemical, nickel-catalyzed synthesis of ketones from carboxylic acid-derived precursors is presented. Hantzsch ester (HE) functions as a cheap, green and strong photoreductant to facilitate radical generation and also engages in the Ni-catalytic cycle to restore the reactive species. With this dual role, HE allows for the coupling of a large variety of radicals (1°,2°, benzylic, α-oxy & α-amino) with aroyl and alkanoyl moieties, a new feature in reactions of this type. With both precursors deriving from abundant carboxylic acids, this protocol is a welcome addition to the organic chemistry toolbox. The reaction proceeds under mild conditions without the need for toxic metal reagents or bases and shows a wide scope, including pharmaceuticals and complex molecular architectures.
