The reactions of aminoguanidine (guanylhydrazine) with 3-deoxy-D-erythro-hexos-2-ulose (1a), 3-deoxy-D-glycero-pentose-2-ulose (1b), D-erythro-hexos-2-ulose (1c), and D-glycero-pentose-2-ulose (1d) were examined at 37 degrees at a solution pH of 7.0 (phosphate buffer). For 1a and 1b, two major products were observed and shown respectively to be the 5- and 6-substituted 3-amino-1,2,4-triazine derivatives. The ratios of the products were independent of the amount of aminoguanidine present or the order of mixing the reagents prior to the experiments. For 1c and 1d, only the 5-substituted triazine derivatives were formed. No evidence for hydrazone or bishydrazone formation was observed.
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http://dx.doi.org/10.1016/s0008-6215(00)90999-6 | DOI Listing |
J Org Chem
January 2025
Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Laboratory of Optic-electric Chemo/Biosensing and Molecular Recognition, Education Department of Guangxi Zhuang Autonomous Region, Guangxi Minzu University, Nanning 530006, China.
A regioselective [3 + 2] annulation of β,γ-alkynyl-α-ketimino esters with 1,3-dicarbonyls is disclosed. A series of -selective dihydrofurans bearing an exocyclic double bond and a quaternary carbon center are accessed without the usage of base. Control and deuterium-labeling experiments have been investigated to probe into the reaction mechanism.
View Article and Find Full Text PDFJ Agric Food Chem
January 2025
Spanish National Research Council (CSIC), Instituto de Ciencia y Tecnología de Alimentos y Nutrición (ICTAN), Jose Antonio Nováis 6 28040, Madrid, Spain.
β-Carbolines (βCs) are bioactive compounds present in foods and biological systems. This work describes the identification, occurrence, and mechanism of formation of 1-acetyl-β-carbolines (1-acetyl-βCs) that result from the reaction of l-tryptophan with the α-dicarbonyl compound methylglyoxal. Two β-carbolines are characterized as 1-acetyl-β-carboline (AβC) and 1-acetyl-β-carboline-3-carboxylic acid (AβC-COOH).
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
School of Life Science and Engineering, School of Chemistry, Southwest Jiaotong University, Chengdu, 610031, China.
Under mild visible light conditions, formates facilitate C-O cleavage the EDA complex and SCS strategy, yielding α-carbonyl alkyl radicals. These radicals then react with olefins under air conditions, leading to the synthesis of diaryl 1,4-dicarbonyl compounds. Mechanistic studies reveal that α-formyloxy ketone is generated by the reaction between α-brominated acetophenone and formates, followed by the formation of the EDA complex.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute of Organic Chemistry, University of Leipzig, 04103 Leipzig, Germany.
The enantioselective synthesis of 1,4-dicarbonyl compounds continues to pose a significant challenge in organic synthesis, and a catalytic process which generates two adjacent stereogenic centers with full stereochemical control is lacking until now. The 1,4-relationship of the functional groups requires an Umpolung strategy as one of the α-carbonyl positions has to be inverted into an electrophilic center to react with a normal enolate. We report herein the highly enantio- and diastereoselective addition of silyl ketene acetals toward electrophilic 1-azaallyl cations to furnish chiral 4-hydrazonoesters, which are masked 1,4-dicarbonyl compounds.
View Article and Find Full Text PDFSynthesis of complex, multiring, spirocyclic, 1,3-dicarbonyl fused, and highly functionalized 5-phenyl-1-azabicyclo[3.1.0]hexanes (ABCH) has been achieved by an intermolecular reaction of 2-(2'-ketoalkyl)-1,3-indandiones or α,γ-diketo esters with (1-azidovinyl)benzenes under transition metal-free conditions.
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