2454-37-7Relevant articles and documents
Mixed-metal MOFs as efficient catalysts for transfer hydrogenation of furfural, levulinic acid and other carbonyl compounds
Karvembu, Ramasamy,Raja, Duraisamy Senthil,Sindhuja, Dharmalingam,Swaminathan, Srividya,Vasanthakumar, Punitharaj
, (2021/11/22)
Crystalline, porous Fe-Ni mixed-metal metal-organic frameworks (MOFs), namely MIL-88B(Fe2Ni) and NH2-MIL-88B(Fe2Ni), were synthesized and characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, atomic absorption spectrophotometry (AAS) and nitrogen physisorption measurements. The MOFs were then employed as catalysts for transfer hydrogenation (TH) of biomass derivatives such as furfural and levulinic acid, and various other carbonyl compounds using 2-propanol as a sacrificial hydrogen donor. These heterogeneous catalysts are deemed to be environmentally benign, efficient and recyclable. NH2-MIL-88B(Fe2Ni) showcased good catalytic activity with low catalyst loading in short reaction time. The catalysts were recovered and reused several times without significant degradation in catalytic activity. A mechanism for the TH reaction was also proposed. As far as we are aware, this is the first report on the synthesis of furfuryl alcohol and γ-valerolactone (GVL) via TH reaction in just 60 min using a MOF catalyst.
Reduction of carbonyl compounds via hydrosilylation catalyzed by well-defined PNP-Mn(I) hydride complexes
Weber, Stefan,Iebed, Dina,Glatz, Mathias,Kirchner, Karl
, p. 635 - 639 (2021/06/17)
Reduction reactions of unsaturated compounds are fundamental transformations in synthetic chemistry. In this context, the reduction of polarized double bonds such as carbonyl or C=C motifs can be achieved by hydrogenation reactions. We describe here a highly chemoselective Mn(I)-based PNP pincer catalyst for the hydrosilylation of aldehydes and ketones employing polymethylhydrosiloxane (PMHS) as inexpensive hydrogen donor. Graphic abstract: [Figure not available: see fulltext.]
Rhodium-Catalyzed Regiodivergent Synthesis of Alkylboronates via Deoxygenative Hydroboration of Aryl Ketones: Mechanism and Origin of Selectivities
Zhang, Bing,Xu, Xin,Tao, Lei,Lin, Zhenyang,Zhao, Wanxiang
, p. 9495 - 9505 (2021/08/04)
Here, we report an efficient rhodium-catalyzed deoxygenative borylation of ketones to synthesize alkylboronates, in which the regioselectivity can be switched by the choice of the ligand. The linear alkylboronates were obtained exclusively in the presence of P(nBu)3, and PPh2Me favored the formation of branched alkylboronates. The protocol also allows access to 1,1,2-triboronates from the readily available ketones. Mechanistic studies suggest that this Rh-catalyzed deoxygenative borylation of ketones goes through an alkene intermediate, which undergoes regiodivergent hydroboration to afford linear and branched alkylboronates. The different steric effects of PPh2Me and P(nBu)3 were found to be responsible for product selectivity by density functional theory calculations. The alkene intermediate can alternatively undergo sequential dehydrogenative borylation and hydroboration to deliver the triboronates.
