Oxidative alkene difunctionalization reactions are important in synthetic organic chemistry because they can install polar functional groups onto simple non-polar alkene moieties. Many of the most common methods for these reactions rely upon the reactivity of pre-oxidized electrophilic heteroatom donors that can often be unstable, explosive, or difficult to handle. Herein, we describe a method for alkene oxyamination and diamination that utilizes simple carbamate and urea groups as nucleophilic heteroatom donors. This method uses a tandem copper-photoredox catalyst system that is operationally convenient. The identity of the terminal oxidant is critical in these studies. Ag(I) salts proved to be unique in their ability to turn over the copper cocatalyst without deleteriously impacting the reactivity of the organoradical intermediates.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6369989 | PMC |
| http://dx.doi.org/10.3762/bjoc.15.30 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ruthenium-Catalyzed Remote Trifunctionalization of Non-Activated Alkenes via Cyano Migration and -C(sp)-H Functionalization.
Org Lett
January 2025
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610068, People's Republic of China.
A novel Ru-catalyzed radical-triggered trifunctionalization of hexenenitriles is presented, employing a strategy of remote cyano group migration and -C(sp)-H functionalization. Through remote cyano migration, the alkenyl moiety undergoes difunctionalization to the formation of a benzylic radical intermediate. This intermediate facilitates -selective C-H bond addition relative to the C-Ru bond within the Ru(III) complex, ultimately enabling trifunctionalization.
View Article and Find Full Text PDFVisible-Light-Driven Carboxylative 1,2-Difunctionalization of C=C Bonds with Tetrabutylammonium Oxalate.
ACS Cent Sci
January 2025
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, 209 Tongshan Road, Xuzhou 221004, China.
Herein, we report a visible-light-induced charge-transfer-complex-enabled dicarboxylation and deuterocarboxylation of C=C bonds with oxalate as a masked CO source under catalyst-free conditions. In this reaction, we disclosed the first example that the tetrabutylammonium oxalate could be able to aggregate with aryl substrates via π-cation interactions to form the charge transfer complexes, which subsequently triggers the single electron transfer from the oxalic dianion to the ammonium countercation under irradiation of 450 nm bule LEDs, releasing CO and CO radical anions. Diverse alkenes, dienes, trienes, and indoles, including challenging trisubstituted olefins, underwent dicarboxylation and anti-Markovnikov deuterocarboxylation with high selectivity to access valuable 1,2- and 1,4-dicarboxylic acids as well as indoline-derived diacids and β-deuterocarboxylic acids under mild conditions.
View Article and Find Full Text PDFRecent progress in the organoselenium-catalyzed difunctionalization of alkenes.
Org Biomol Chem
January 2025
School of Pharmacy, Nantong Key Laboratory of Small Molecular Drug Innovation and Jiangsu Province Key Laboratory for Inflammation and Molecular Drug Target, Nantong University, Nantong 226019, People's Republic of China.
Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing to their intrinsic advantages, including low cost, low toxicity, stability in both air and water, and strong compatibility with diverse functional groups. The difunctionalization of alkenes-the process of incorporating two functional groups onto a carbon-carbon double bond-has garnered particular interest within the chemical community owing to its significant applications in organic synthesis. Recently, organoselenium-catalyzed difunctionalization of alkenes has emerged as an ideal and powerful route to obtain high-value vicinal difunctionalized molecules.
View Article and Find Full Text PDFPhotoredox radical/polar crossover enables carbo-heterofunctionalization of alkenes: facile access to 1,3-difunctionalized nitro compounds.
Chem Commun (Camb)
January 2025
Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland.
Herein, we present an efficient and practical method for multicomponent carbo-heterofunctionalization of alkenes radical-polar crossover photoredox catalysis. Employing geminal bromonitroalkanes as redox-active reagents with a wide range of O-centered nucleophiles allows rapid access to various 1,3-difunctionalized nitro compounds, including β-nitro ketones, 1,3-nitro alcohols, 1,3-nitro ethers as well as cyclic molecules.
View Article and Find Full Text PDFPhotocatalyzed Azidofunctionalization of Alkenes via Radical-Polar Crossover.
Angew Chem Int Ed Engl
January 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!