768-59-2Relevant articles and documents
Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
supporting information, p. 9029 - 9039 (2021/06/28)
Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
Selective hydrogenation of primary amides and cyclic di-peptides under Ru-catalysis
Subaramanian, Murugan,Sivakumar, Ganesan,Babu, Jessin K.,Balaraman, Ekambaram
supporting information, p. 12411 - 12414 (2020/10/30)
A ruthenium(II)-catalyzed selective hydrogenation of challenging primary amides and cyclic di-peptides to their corresponding primary alcohols and amino alcohols, respectively, is reported. The hydrogenation reaction operates under mild and eco-benign conditions and can be scaled-up.
Hydrosilylation of carbonyl and carboxyl groups catalysed by Mn(i) complexes bearing triazole ligands
Martínez-Ferraté, Oriol,Chatterjee, Basujit,Werlé, Christophe,Leitner, Walter
, p. 6370 - 6378 (2019/11/20)
Manganese(i) complexes bearing triazole ligands are reported as catalysts for the hydrosilylation of carbonyl and carboxyl compounds. The desired reaction proceeds readily at 80 °C within 3 hours at catalyst loadings as low as 0.25 to 1 mol%. Hence, good to excellent yields of alcohols could be obtained for a wide range of substrates including ketones, esters, and carboxylic acids illustrating the versatility of the metal/ligand combination.
