The synthesis of alkyl halides can be performed by simply halide exchange reactions between two different alkyl halides, catalyzed by aluminosilicates. Here, we show that commercially available alumina shows a superior catalytic activity for the halogen exchange reaction between long alkyl halides (more than 6 carbons), including fluorides, in either batch or flow modes. The catalytic activity of the solid alumina is modulated by alkaline countercations on the surface, and sodium-supported alumina shows the optimal performance for the iodo-bromo and iodo-fluoro exchange under inflow reaction conditions, after >24 h reaction time, without any external additive.
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http://dx.doi.org/10.1021/acsorginorgau.4c00039 | DOI Listing |
Org Lett
January 2025
Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, Wisconsin 53706, United States.
Although alkyl alcohols and aryl chlorides are the two most abundant substrate pools for cross-electrophile coupling, methods to couple them remain limited. Herein we demonstrate a simple procedure for the in situ deoxychlorination of alcohols followed by XEC with aryl chlorides. A broad substrate scope can be achieved by tuning the rate of the reaction via halide exchange.
View Article and Find Full Text PDFChemistry
January 2025
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China.
We have developed an efficient synthesis of fluoroalkenes via tandem electrochemical dehalogenation-elimination protocol. The key step is the generation of carbon anion by electrochemical reductive dehalogenation of alkyl halides. Various gem-difluoroalkenes and monofluoroalkenes were prepared in moderate to good yields from α-difluoromethylated/α-trifluoromethylated benzyl halides.
View Article and Find Full Text PDFJ Org Chem
January 2025
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China.
In the vanguard of sustainable chemistry, the pursuit of efficient pathways for the synthesis of alkyl bicyclo[1.1.1]pentane-heteroaryls has captured the attention of the scientific vanguard.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi, 330031, China.
We present a highly efficient and versatile nickel-catalyzed protocol for the reductive cross-coupling of unactivated CFH-substituted electrophiles with a wide variety of aryl and alkenyl halides. This novel approach offers high catalytic reactivity and broad functional group compatibility, enabling late-stage fluoroalkylation of drug molecules.
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