Progress in the transition-metal-catalyzed or -free fluoroalkylation of diazo compounds with different types of fluoroalkyl (R ) transfer reagents is summarized in this review. Special attention is focused on the straightforward trifluoromethylation, gem-difluoroolefination, trifluoromethoxylation, fluoroalkylthiolation, and trifluoromethylselenolation of diazo substrates. The mechanistic insights and the application of some of the products are also discussed in this article. We believe that this review will inspire both young and experienced chemists to further study the direct fluoroalkylation of diazo compounds as an efficient and convenient way to build complex fluorine-containing molecules.
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http://dx.doi.org/10.1002/asia.202000305 | DOI Listing |
Beilstein J Org Chem
February 2024
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China.
An efficient multicomponent reaction of newly designed β-trifluoromethyl β-diazo esters, acetonitrile, and carboxylic acids via an interrupted esterification process under copper-catalyzed conditions has been developed, which affords various unsymmetrical β-trifluoromethyl ,-diacyl-β-amino esters in good to excellent yields. The reaction features mild conditions, a wide scope of β-amino esters and carboxylic acids, and also applicability to large-scale synthesis, thus providing an efficient way for the synthesis of β-trifluoromethyl β-diacylamino esters. Furthermore, this reaction represents the first example of a Mumm rearrangement of β-trifluoromethyl β-diazo esters.
View Article and Find Full Text PDFOrg Lett
May 2023
Institute of Advanced Studies and School of Pharmaceutical Sciences, Taizhou University, Jiaojiang 318000, Zhejiang, China.
We disclose herein an efficient photochemical formal [3+2+1] annulation strategy for the transformation of diazocarbonyl compounds into various fluorinated nitrogen-containing heterocycles. This transformation is characterized by reacting fluoroalkyl radicals with α-diazoketones, which are used as infrequent denitrogenated synthons under visible light. Moreover, a wide range of N-heterocycles containing precious CF and perfluoroalkylated groups are constructed in moderate to good yields.
View Article and Find Full Text PDFOrg Lett
December 2022
Jilin Province Key Laboratory of Organic Functional Molecular Design and Synthesis, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
Herein we describe the pioneering Rh-catalyzed coupling reactions of a fluoroalkyl carbene with azides to access α-trifluoroethylated imines, where fluoroalkyl -sulfonylhydrazones are used as fluoroalkyl diazo surrogates. Remarkably, using TMSN as the N source, two C-N bond formation products were obtained. Furthermore, the α-trifluoroethylated imine products could be easily reduced to the corresponding -trifluoroethylated anilines.
View Article and Find Full Text PDFAcc Chem Res
June 2022
Department of Chemistry, Northeast Normal University, Changchun 130024, China.
Over recent decades, -sulfonylhydrazones have attracted significant attention in academic and industrial contexts owing to their ease of preparation, versatile reactivity, high stability, and practicality. In particular, the use of -sulfonylhydrazones as precursors for diazo compounds has paved the way for innovative and original organic reactions that are otherwise difficult to achieve. Three key developments are noteworthy in the history of -sulfonylhydrazone chemistry: (1) Bamford and Stevens initially disclosed the application of -tosylhydrazones as a diazo source in 1952; (2) Aggarwal and co-workers investigated -tosylhydrazone salts as diazo precursors for sulfur ylide-mediated asymmetric epoxidation and aziridination in 2001; and (3) Barluenga, Valdés and co-workers first reported Pd-catalyzed cross-coupling reactions with -tosylhydrazones in 2007, thus introducing the direct use of -tosylhydrazones in carbene transfer reactions.
View Article and Find Full Text PDFChem Commun (Camb)
May 2021
College of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of Technology, 2055 N. Yan'an Avenue, Changchun 130012, P. R. China.
A simple and practical method for the azidation of β-fluoroalkyl α,β-unsaturated ketones to access a wide variety of fluorinated nitrogenous carbonyl compounds is developed. Different from existing precedents, neither a metallic nor an organic catalyst was involved in our strategy. Judicious choice of solvents allows for the modulation of the reaction outcomes, delivering β-azido ketones or β-amino α-diazo ketones.
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