Transition metal coordination chemistry and catalysis are rife with phosphine ligands. One of the rather less studied members of the phosphine ligand family are phosphine aldehydes. We have synthesised 3-(diphenylphosphino)propanal (PCHO) with a slight modification of the known procedure and studied its complexation behaviour with palladium(II) and platinum(II). The catalytic activity of the palladium(II) phosphine aldehyde complexes was investigated in Cu-free Sonogashira and Suzuki-Miyaura cross-coupling reactions. Furthermore, the homogeneous nature of the catalytically active species was confirmed.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d3dt00507k | DOI Listing |
Org Lett
January 2025
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.
The photocatalytic alkene-migrative chain elongation reaction of 2-phosphinostyrenes with aldehydes under mild conditions in response to blue light was demonstrated. A broad range of aldehydes, both aliphatic and aromatic, participated in this reaction to afford alkene-phosphine oxides in a -selective manner. Mechanistic experiments suggested the formation of benzophospholene-based ylide intermediates via photocatalytic cyclization of phosphinostyrenes followed by solvent-mediated proton transfer under base-free reaction conditions.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Basic Education, Shanxi Agricultural University, Jinzhong, Shanxi 030801, P. R. China.
DFT calculations have been performed to gain insight into the mechanism of hydrocarbonylation of olefins and the origin of regio- and chemoselectivity. It is shown that the most feasible mechanism involves five steps: (i) decomposition of acetic formic anhydride, (ii) hydropalladation of olefins, (iii) CO migratory insertion, (iv) iodide-assisted acetate-formate exchange, and (v) formylation or carboxylation. Importantly, carboxylation proceeds via the decomposition of anhydride, followed by reductive elimination instead of direct hydrolysis of anhydride.
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 PDFAcc Chem Res
November 2024
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China.
J Am Chem Soc
November 2024
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!