Hyptatic acid-A (32), a 2alpha,3beta,24-trihydroxyolean-12-en-28-oic acid, previously isolated from Hyptis capitata, was obtained from maslinic acid (2). The regioselective cyclopalladation of the axial methyl group on C-4 of maslinic acid afforded the C-24 hydroxymethylene group due to the presence of a C-2-OR substituent. Nevertheless, hederagenin (7) (23-hydroxy derivative) was formed when this oxygenated group was not present.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/jo070116e | DOI Listing |
Organometallics
August 2023
Faculty of Chemical Technology, Institute of Organic Chemistry and Technology, University of Pardubice, Studentská 573, 53210 Pardubice, Czech Republic.
Palladacycles are key intermediates in catalytic C-H bond functionalization reactions and important precatalysts for cross-couplings. It is commonly believed that palladacycle formation occurs through the reaction of a substrate bearing a C-H bond to a suitable metal-directing group for interaction with, typically, mononuclear "Pd(OAc)" species, with cyclopalladation liberating acetic acid as the side product. In this study, we show that ,-dimethyl-fluoro-benzyl amines, which can be cyclopalladated either or to fluorine affording two regioisomeric products, can occur by a direct reaction of Pd(OAc), proceeding via higher-order cyclopalladated intermediates.
View Article and Find Full Text PDFDalton Trans
August 2023
Institute of Organic Chemistry and Technology, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210 Pardubice, The Czech Republic.
Simple switching of the site-selectivity of C-H activation reactions of substrates containing multiple directing groups is particularly important for the so-called late stage functionalization synthetic approach. In this work, we verified the possibility of achieving this by adding acids of different strengths. Using a substrate containing two differently strong (and basic) directing groups, the influence of the addition of acids on the regioselectivity of the C-H activation step of the reaction with palladium acetate was thoroughly studied.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2022
Departamento de Química Orgánica, Facultad de Ciencias, and Center for Innovation in Advanced Chemistry (ORFEO-CINQA, Universidad Autónoma de Madrid (UAM) Cantoblanco, 28049, Madrid, Spain.
The selective δ-C(sp )-H acetoxylation of N-(SO Py)-protected amino acid derivatives has been accomplished by using palladium-catalysis and PhI(OAc) (PIDA) as both terminal oxidant and acetoxy source. The distinct structural and electronic features of the SO Py compared to more traditional carbonyl-based directing groups is essential to override the otherwise more favourable competitive intramolecular C-H amination. The δ-site selectivity predominates over traditionally more favorable 5-membered cyclopalladation at competitive γ-CH .
View Article and Find Full Text PDFAcc Chem Res
August 2022
State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.
Catalytic C-N bond cross-coupling reactions have been a subject of fundamental importance in synthetic organic and medicinal chemistry because amides and amines are ubiquitous motifs in natural products, functional materials, and pharmaceuticals. Since the pioneering works of Breslow and Mansuy on the metalloporphyrin-catalyzed direct hydrocarbon amidation using sulfonyliminoiodinane reagents, substantial development has been achieved toward practical and selective amination protocols. Notably, Du Bois's group developed the dirhodium(II,II) carboxylate catalytic system for direct C(sp)-H amidations via Rh-sulfonyl nitrene intermediates.
View Article and Find Full Text PDFNat Commun
January 2021
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Heteroarenes containing carbon-silicon (C-Si) bonds are important building blocks that play an important role in the construction of natural products, pharmaceuticals, and organic materials. In this context, the C-H silylation of heteroarenes is a topic of intense interest. Indole C-H silylation can preferentially occur at the nucleophilic C3 and C2 position (pyrrole core), while accessing the C4-C7 positions (benzene core) of the indole remains highly challenging.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!