Copper-catalyzed O-arylation of enolates with diaryliodonium salts as arylating reagents was realized successfully. As important building blocks, β-aryloxy carbonyl compounds were obtained in up to 98% yield under mild conditions, and complete control of O-arylation and Z-stereoselectivity were achieved. The origin of the selectivity was also discussed.
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http://dx.doi.org/10.1021/ol501434d | DOI Listing |
ACS Omega
July 2022
Department of Chemistry, University of California-San Diego, La Jolla, California 92093-0358, United States.
Alkylation of aromatics and formation of a new C-C bond is usually achieved by the electrophilic attack of an activated carbon species on an electron-rich aromatic ring. Herein, we report an alternative method for alkylation of aromatics via nucleophilic addition of enolates of active methylene compounds to 1,4-dehydrobenzene diradicals derived from enediynes cyclodec-1,5-diyne-3-ene, benzo[3,4]-cyclodec-1,5-diyne-3-ene, and cyclohexeno[3,4]-cyclodec-1,5-diyne-3-ene. The benzo-substituted enediyne produces slightly higher yields of alkylation products than do the other two enediynes, but the differences are not substantial.
View Article and Find Full Text PDFJ Org Chem
March 2020
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
The mechanism of the Pd-catalyzed α-arylation of three model enolates is studied focusing on an analysis of their very different reactivities. In particular, the low reactivity of nitronates under standard arylation conditions and their high sensitivity to the nature of catalytic systems are addressed. The three canonical steps for each of the reaction systems are examined, and key trends surrounding the stability of intermediates and transition states are delineated.
View Article and Find Full Text PDFJ Org Chem
October 2017
China International Science and Technology Cooperation Base of Food Nutrition/Safety and Medicinal Chemistry, College of Biotechnology, Tianjin University of Science and Technology, Tianjin 300457, China.
A concise and practical synthetic method has been developed for 8-azachromones, including 8-azaflavones, which have emerged as a promising class of compounds. Using commercially available nicotinates as the starting material, 8-azachromones were obtained in only three steps. The key intramolecular O-arylation reaction was achieved by nucleophilic attack of enolates to C2 of N-oxides under PyBrop or AcO activation conditions.
View Article and Find Full Text PDFOrg Lett
July 2014
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science , 345 Lingling Road, Shanghai 200032, China.
Copper-catalyzed O-arylation of enolates with diaryliodonium salts as arylating reagents was realized successfully. As important building blocks, β-aryloxy carbonyl compounds were obtained in up to 98% yield under mild conditions, and complete control of O-arylation and Z-stereoselectivity were achieved. The origin of the selectivity was also discussed.
View Article and Find Full Text PDFOrg Lett
December 2004
Department of Chemistry, University of Bath, Bath BA2 7AY, UK.
[reaction: see text] A catalyst generated from Pd2(dba)3 and the ligand DPEphos effects intramolecular C-O bond formation between enolates and aryl halides in the conversion of 1-(2-haloaryl)ketones directly into the corresponding benzofurans. Both cyclic and acyclic ketones are efficient substrates. Thio ketones can also be employed allowing the preparation of the corresponding benzothiophenes.
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