[reaction: see text] A highly selective catalytic reductive isomerization reaction is described. The extremely mild and neutral reaction conditions (10% Pd/C, H2, and MeOH at 0 degrees C) tolerate a wide range of functional groups and generally result in excellent yields. Mechanistic studies suggest that this reaction does not proceed via a stepwise reduction/elimination sequence or a pi-allylpalladium intermediate.
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http://dx.doi.org/10.1021/ol050952f | DOI Listing |
Nat Commun
January 2025
Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Avenue, 210023, Nanjing, China.
Sulfur-containing units are fundamental components widely found in bioactive compounds, prompting notable efforts toward developing synthetic methodologies for incorporating sulfur functionality into organic precursors. The synthesis of sulfinate esters and sulfinamides has garnered significant interest owing to their immense potential for applications, especially in drug development. However, most existing synthetic protocols suffer from some limitations.
View Article and Find Full Text PDFInorg Chem
January 2025
Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo 19, Murcia 30100, Spain.
Unsymmetrical bis-cyclometalated dicarboxylato complexes (-6-32)-[Pt(tpy)(OCR)] [tpy = cyclometalated 2-(-tolyl)pyridine, R = -Bu (), Me (), Ph (), CF ()], are obtained from the reaction of -[Pt(tpy)] with the appropriate PhI(OCR) reagent. Treatment of complexes of this type with different carboxylates (R'CO) results in the formation of mixed-carboxylato derivatives, namely (-6-43)-[Pt(tpy)(OCMe)(OCR')] [R' = -Bu (), CF (), Ph ()], (-6-34)-[Pt(tpy)(OCCF)(OCR')] [R' = -Bu (), Me (), Ph ()], and (-6-34)-[Pt(tpy)(OC--Bu)(OCMe)] (). Irradiation of - and - with UV light (365 nm) in MeCN gives 5-methyl-2-(2-pyridyl)phenyl pivalate (), 5-methyl-2-(2-pyridyl)phenyl acetate () or 5-methyl-2-(2-pyridyl)phenyl benzoate () as the major photoproduct from most complexes, resulting from a reductive C-O coupling between a tpy ligand and a carboxylato ligand.
View Article and Find Full Text PDFJ Org Chem
December 2024
State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China.
Silyl-phenanthroline (NN'Si) ligand ancillary iridium-catalyzed C(sp)-H borylation is investigated theoretically. Density functional theory calculations clearly disclose that the (NN'Si)Ir(H)(Bpin) (NN'Si = 6-[(di--butylsilyl)methyl]-1,10-phenanthroline) complex is a resting state, and the (NN'Si)Ir(Bpin) complex serves as an active species in the catalytic cycle. The remarkably high activity of this type of a catalyst arises from the rapid reductive elimination of HBpin from (NN'Si)Ir(H)(Bpin) to generate the active species (NN'Si)Ir(Bpin).
View Article and Find Full Text PDFNat Commun
November 2024
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Composite Materials, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai, China.
D-amino acids, found in excess in a minority of organisms and crucial for marine invertebrates, contrast with the more common L-amino acids in most life forms. The local prebiotic origin of D-amino acid enantiomeric excess in natural systems remains an unsolved conundrum. Herein, we demonstrate the formation of enantiomeric excess (ee) D-amino acids through photocatalytic reductive amination of α-keto acids on natural pyrite.
View Article and Find Full Text PDFRSC Adv
November 2024
Dept. of Chemistry, School of Advanced Sciences, Vellore Institute of Technology Chennai Campus, Vandalur-Kelambakkam Road Chennai 600127 Tamil Nadu India +91 44 3993 2555 +91 44 3993 1479.
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