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A copper-mediated cross-coupling reaction between a diazo compound and a sodium alkane(arene)sulfinate gives a sulfone as the product. This reaction proceeds under mild conditions and features excellent functional group compatibility. A wide range of sodium alkane(arene)sulfinates were successfully applied in this chemistry. Mechanistic studies revealed that the overall reaction efficiency of the sulfinates was in line with their nucleophilicity in this reaction.
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http://dx.doi.org/10.1021/acs.orglett.1c02481 | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry, Rice University, Houston, Texas 77005, United States.
Pyroglutamate is a cyclic -terminal post-translational modification that occurs in both proteins and peptide hormones. The prevalence and biological roles of pyroglutamate are little understood, in part due to limited tools to identify, quantify, and manipulate its pyrrolidinone structure. Selective modification of pyroglutamate residues in complex polypeptides may provide unique tools to better understand its biological roles and to allow late-stage diversification of biologically active pyroglutamate-containing sequences.
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December 2024
Laboratory of Analytical and Bioinorganic Chemistry, Division of Analytical and Physical Sciences, Kyoto Pharmaceutical University, 5 Nakauchi-cho, Misasagi, Yamashina-ku, Kyoto, 607-8414, Japan.
The copper-catalyzed Chan-Evans-Lam (CEL) coupling reaction advances carbon-heteroatom cross-coupling and has facilitated the development of radiohalogenation methodologies in radiochemistry. This study investigated the mechanisms and side reactions of CEL iodination under conditions relevant to radiosynthesis and typical organic synthesis, focusing on the effects of sodium iodide. The concentrations of copper and iodide, as well as the copper-to-iodide ratio, were identified as significant factors for successful copper-mediated CEL iodination, influencing the reaction mechanisms and side reactions.
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October 2024
CNRS, Bordeaux INP, ISM, UMR 5255, University of Bordeaux, F-33400, Talence, France.
J Org Chem
July 2024
Department of Chemistry, Chungnam National University, Daejeon 34134, Republic of Korea.
A palladium-catalyzed/copper-mediated cross-coupling of -pyrimidinyl thioesters with arylboronic acids to yield biaryls is described. The reaction is likely to proceed via cleavage of the S-C(O) bond and subsequent release of CO, rather than via cleavage of the S-C(pyrimidine) bond and release of SCO, as supported by the results of both experimental and computational studies. The investigation of the reaction scope with various -pyrimidinyl thioesters and arylboronic acids showed that the reaction is significantly affected by the substituent of the thioester and the presence of a chelatable substituent was found to increase reaction efficiency.
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November 2023
Department of Chemistry, University of Michigan 930 North University Avenue Ann Arbor Michigan 48109 USA
This report describes a net C-H radiocyanation reaction for the transformation of electron rich (hetero)aromatic substrates into CN-labeled products. Electrophilic C(sp)-H iodination of the (hetero)arene with -iodosuccinimide is followed by Cu-mediated radiocyanation with KCN. This sequence is applied to a variety of substrates, including the nucleobases uracil and cytosine, the amino acids tyrosine and tryptophan, and the peptide LYRAGWRAFS, which undergoes selective C-H radiocyanation at the tryptophan (W) residue.
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