Invited for the cover of this issue are Ken Sakata, Yoshiaki Nishibayashi, and co-workers at The University of Tokyo and Toho University. The image depicts the propargylic substitution reaction of a propargylic alcohol with an N-monosubstituted hydrazone, where the nucleophilicity of the hydrazone is controlled by the choice of catalytic system. Read the full text of the article at 10.1002/chem.202103287.
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http://dx.doi.org/10.1002/chem.202103784 | DOI Listing |
J Org Chem
January 2025
College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China.
A facile copper-catalyzed, base-controlled cyclization reaction has been developed for the synthesis of 9-membered cycloalkyne and 6-membered heterocycle sultams under mild conditions. This protocol utilizes a copper-catalyzed intramolecular A (alkyne-aldehyde-amine) coupling reaction to efficiently synthesize 9-membered cycloalkyne sultams in yields up to 90%. Alternatively, by substituting NaHCO with DBU, the protocol achieves selective deprotection of the -propargyl group, thereby facilitating the formation of 6-membered heterocyclic sultams, also in high yields.
View Article and Find Full Text PDFJ Org Chem
January 2025
State Key Laboratory of Functions and Applications of Medicinal Plants, Guizhou Medical University, 3491 Gaohai Road, Guiyang 550014, P. R. China.
A copper-catalyzed regioselective annulation reaction, conducted without ligands or oxidants, has been developed for the preparation of multisubstituted furans from the readily available starting materials, β-keto esters and propargyl acetates. This process accommodates a wide range of functional groups, resulting in furan skeletons with diverse substitution patterns. The method's potential synthetic utility is highlighted by its applicability in gram-scale preparations and late-stage modifications of natural products.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
A method for synthesizing allenylselenides has been developed using readily available propargyl carbonate and phenylselenol. The reaction is catalyzed by Ni(II) and proceeds a migratory insertion and β-oxygen elimination mechanism. Due to the strong interaction between Se and Ni leading to catalyst deactivation, zinc salt was used to mitigate the deleterious effects of Se anions on the catalyst, thereby facilitating the successful synthesis of the target products.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, Technische Universität Darmstadt, Peter-Grünberg-Straße 8, 64287 Darmstadt, Germany.
Hyperpolarization of small peptides by parahydrogen-induced polarization (PHIP) to increase the sensitivity of nuclear magnetic resonance (NMR) techniques is well established, while its application to larger biopolymers is still a mainly unexplored area. A particular challenge is the presence of folding-essential disulfide bridges. They tend to form metal complexes, thus hampering catalytic hydrogenation, a prerequisite for PHIP.
View Article and Find Full Text PDFOrg Lett
December 2024
State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203, China.
The fused eight-membered carbocycles (EMCs) play vital roles in the medicinal and biological investigations of many natural products and marketed drugs. The traditional synthesis of [6-8-6] benzo-fused derivatives involves multistep reactions and low yields, making the development of a one-step synthesis method a more challenging work. Here, we present a novel strategy for one-step construction of [6-8-6] benzo-fused scaffold from propargyl diazoacetates substituted with benzyl-nitrogen heterocyclic ring via Rh(ll)-catalyzed carbene/alkyne metathesis (CAM) and selective C-H bond insertion.
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