The first time application of hydroformylation on olefinic derivatives of isosorbide and isomannide is shown by which a new carbon-carbon bond is formed. Depending on the ligand and reaction conditions used, the C6 regioisomer a can be obtained in 4:1 ratio and excellent yield, whereas C5 isomer b is achieved in almost complete regioselectivity (46:1) and good yield. In the majority of cases only the exo orientation is observed for the obtained aldehydes, and the method is easily applicable also on a 1 g scale.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.joc.6b01179 | DOI Listing |
Acc Chem Res
January 2025
Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
ConspectusFor chemical reactions with complex pathways, it is extremely difficult to adjust the catalytic performance. The previous strategies on this issue mainly focused on modifying the fine structures of the catalysts, including optimization of the geometric/electronic structure of the metal nanoparticles (NPs), regulation of the chemical composition/morphology of the supports, and/or adjustment of the metal-support interactions to modulate the reaction kinetics on the catalyst surface. Although significant advances have been achieved, the catalytic performance is still unsatisfactory.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Substituting the molecular metal complexes used in the industrial olefin hydroformylation process is of great significance in fundamental research and practical application. One of the major difficulties in replacing the classic molecular metal catalysts with supported metal catalysts is the low chemoselectivity and regioselectivity of the supported metal catalysts because of the lack of a well-defined coordination environment of the metal active sites. In this work, we have systematically studied the influences of key factors (crystallinity, alkali promoters, etc.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
Methanolation of olefins is introduced as a new low-pressure synthetic pathway to C1 elongated alcohols. Formally, HCOH is added to the C=C bond in a 100 % atom efficient manner. Mechanistically, the overall transformation occurs as a tandem reaction sequence by combining the dehydrogenation of methanol to syngas at a CO : H ratio of 1 : 2 with subsequent hydroformylation to the corresponding aldehyde and its final hydrogenation to the alcohol.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Centre for Membrane Separations, Adsorption, Catalysis and Spectroscopy for Sustainable Solutions (cMACS), KU Leuven, Celestijnenlaan 200F p.o. box 2454, 3001, Leuven, Belgium.
The valorization of carbon dioxide as a C1 building block in C-C bond forming reactions is a critical link on the road to carbon-circular chemistry. Activation of this inert molecule through reduction with H to carbon monoxide in the reverse water-gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite-based compartmentalized approach.
View Article and Find Full Text PDFACS Catal
August 2024
Department of Chemistry, University of Warwick, Coventry CV4 7AL, U.K.
Synthesis of a chelating phosphite-phosphine ligand from a tris(quinoxaline) extended resorcin[4]arene and its application in the rhodium-catalyzed hydroformylation of terminal alkyl alkenes are reported. Rhodium complexes are formed within the cavity of the macrocycle and branched-selective hydroformylation of 1-octene with a / ratio of 5.9 has been achieved at 60 °C under 1:1 H/CO (20 bar).
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!