The asymmetric synthesis of 3-indolylglycine derivatives was achieved by an oxidative heterocoupling reaction. This method for the selective C-3 functionalization of unprotected indoles with the chiral equivalent of a nucleophilic glycine nickel(II) complex afforded adducts with high diastereoselectivities. The decomposition of adducts readily afforded 3-indolylglycine derivatives in high yields.
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http://dx.doi.org/10.1039/c3cc38908a | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Nankai University, SKLEOC, 300071, Tianjin, CHINA.
Amino groups are abundant in both natural and synthetic molecules, offering highly accessible sites for modifying native biorelevant molecules. Despite significant progress with more reactive thiol groups, methods for connecting two amino groups with reversible linkers for bioconjugation applications remain elusive. Herein, we report the use of oxidative decarboxylative condensation of glyoxylic acid to crosslink two alkyl amines via a compact formamidine linkage, applicable in both intra- and intermolecular contexts.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Institut für Organische Chemie, Universität Regensburg, Universitätsstrasse 31, 93053, Regensburg, Germany.
We disclose a mediated electrochemical [2+2+2] annulation of alkynes with nitriles, forming substituted pyridines in a single step from low-cost, readily available starting materials. The combination of electrochemistry and a triarylamine redox mediator obviates the requirements of transition metals and additional oxidants. Besides the formation of diarylpyridine moieties via the homocoupling of two identical alkynes, the heterocoupling of two different alkynes depending on their electronic nature is possible, highlighting the unprecedented control of chemoselectivity in this catalytic [2+2+2] process.
View Article and Find Full Text PDFPhotosensitizer (PS)-mediated generation of singlet oxygen, O (aΔ) is a well-explored phenomenon in chemistry and biology. However, the requirement of appropriate PSs with optimum excited state properties is a prerequisite for this approach which limits its widespread application. Herein, we report the generation of O (aΔ) direct charge-transfer (CT) excitation of the solvent-O (XΣ ) collision complex without any PS and utilize it for the catalyst-free oxidative coupling of arylamines to azoaromatics under ambient conditions in aqueous medium.
View Article and Find Full Text PDFOrg Lett
June 2024
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
The first total syntheses of glycoborinine, clausenawalline A, and clausenawalline E were achieved. The key step employed a vanadium-catalyzed oxidative coupling of two hydroxycarbazole monomers. High-throughput experimentation was used to identify conditions favoring selective heterocoupling of these monomers that possess similar redox potentials.
View Article and Find Full Text PDFNat Chem
October 2024
Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo, Japan.
Anaerobic ammonium oxidation (anammox)-the biological process that activates ammonium with nitrite-is responsible for a significant fraction of N production in marine environments. Despite decades of biochemical research, however, no synthetic models capable of anammox have been identified. Here we report that a copper sulfide mineral replicates the entire biological anammox pathway catalysed by three metalloenzymes.
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