A mild and efficient protocol for O-arylation of alcohols and phenols (ROH) by triarylsulfonium triflates was developed under transition-metal-free conditions. Various alcohols, including primary, secondary and tertiary, and phenols bearing either electron-donating or electron-withdrawing groups on the aryl rings were smoothly converted to form the corresponding aromatic ethers in moderate to excellent yields. The reactions were conducted at 50 or 80 °C for 24 h in the presence of a certain base and showed good functional group tolerance. The base-mediated arylation with asymmetric triarylsulfonium salts could selectively transfer the aryl groups of sulfoniums to ROH, depending on their inherent electronic nature. The mechanistic studies revealed that the reaction might proceed through the nucleophilic attack of the in situ formed alkoxy or phenoxy anions at the aromatic carbon atoms of the C-S bonds of triarylsulfonium cations to furnish the target products.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/asia.201900968 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Nickel-Catalyzed O-Arylation of N-Protected Amino Alcohols with (Hetero)aryl Chlorides.
Chemistry
November 2024
Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. Box 15000, Halifax, Nova Scotia, B3H 4R2, Canada.
The aryloxyamine motif is a prominent pharmacophore in drug design and development. While these biologically relevant structures could in principle be sustainably assembled from the base metal-catalyzed O-arylation of inexpensive and abundant amino alcohols with (hetero)aryl chlorides, reports of such challenging C-O bond formations with useful scope are lacking. In response, we report herein the hitherto unknown Ni-catalyzed C-O cross-coupling of N-protected amino alcohols (primary, secondary, and tertiary) with (hetero)aryl chlorides.
View Article and Find Full Text PDFBase-mediated synthesis of aryl enol ethers from α-aryl allylic alcohols and arylsulfonium salts.
Org Biomol Chem
October 2024
School of Chemistry, Chemical Engineering and Life Science, Hubei Key Laboratory of Nanomedicine for Neurodegenerative Diseases, Wuhan University of Technology, Wuhan 430070, China.
A concise synthesis of aryl enol ethers from allylic alcohols and arylsulfonium salts by simply using an inorganic base as a mediator is described. The reaction enabled the facile conversion of various α-aryl allylic alcohols into the corresponding aryl enol ethers in good yields with excellent selectivity. The results demonstrated that both symmetric triarylsulfonium triflate and 10-methyl-5-aryl-5,10-dihydrophenothiazin-5-ium salts were effective arylation reagents for the base-initiated selective -arylation and isomerization of α-aryl allylic alcohols.
View Article and Find Full Text PDFPd(0)/Xantphos-Catalyzed Benzylic C(sp)-O Arylation of Benzyl Heteroaryl Ethers: Reduction of Pd(II) to Pd(0) by Xantphos.
J Org Chem
September 2024
College of Chemistry, National Engineering Research Center of Pesticide, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
Herein, we report the synthesis of 1,1-diarylmethanes via palladium-catalyzed benzylic C(sp)-O arylation of benzyl alcohol derivatives. An efficient, straightforward approach to synthesizing Pd(0)(xantphos) was developed through in situ reduction of Pd(II) to Pd(0) with the bidentate tertiary phosphine xantphos, which proved to be a highly active precatalyst in the Suzuki-Miyaura cross-coupling reaction of benzyl heteroaryl ethers.
View Article and Find Full Text PDFURJC-1: Stable and Efficient Catalyst for O-Arylation Cross-Coupling.
Nanomaterials (Basel)
June 2024
Chemical and Environmental Engineering Group, ESCET, Rey Juan Carlos University, C/Tulipán s/n, 28933 Móstoles, Spain.
The design of metal-organic frameworks (MOFs) allows the definition of properties for their final application in small-scale heterogeneous catalysis. Incorporating various catalytic centers within a single structure can produce a synergistic effect, which is particularly intriguing for cross-coupling reactions. The URJC-1 material exhibits catalytic duality: the metal centers act as Lewis acid centers, while the nitrogen atoms of the organic ligand must behave as basic centers.
View Article and Find Full Text PDFCu-Catalyzed Amination of Base-Sensitive Aryl Bromides and the Chemoselective N- and O-Arylation of Amino Alcohols.
J Am Chem Soc
July 2024
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139, United States.
We report a general and functional-group-tolerant method for the Cu-catalyzed amination of base-sensitive aryl bromides including substrates possessing acidic functional groups and small five-membered heteroarenes. The results presented herein substantially expand the scope of Cu-catalyzed C-N coupling reactions. The combination of , an anionic ,-diarylbenzene-1,2-diamine ligand, along with the mild base NaOTMS leads to the formation of a stable yet reactive catalyst that resists deactivation from coordination to heterocycles or charged intermediates.
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!