Recent Progress on Methods for the Preparation of Mono/Di/Trifluoromethoxylation Reagents

doi:10.6023/cjoc202403011

Abstract

Fluorine-containing organic molecules have broad applications in the fields of pharmaceuticals, agrochemicals, and material science. In the pharmaceutical industry, the incorporation of fluorine-containing methoxy groups can enhance the bioavailability and metabolic stability of drugs, while also modulating the stereochemistry and electronic structure of the molecules, thereby improving drug efficacy and selectivity. In the agricultural sector, fluorine-containing organic compounds exhibit significant insecticidal and fungicidal properties. In materials science, fluorine-containing methoxy compounds are widely used in the synthesis and modification of materials, such as batteries, coatings, and catalysts due to their excellent electrochemical performance and thermal stability. Consequently, the efficient introduction of fluorine-containing methoxy groups has become a focal point of research in organic chemistry. This review provides an overview of the preparation methods for monofluoromethoxy (OCH₂F), difluoromethoxy (OCF₂H), and trifluoromethoxy (OCF₃) reagents, as well as the development of trifluoromethoxy reagents.

Key words: monofluoromethoxy reagent, difluoromethoxy reagent, trifluoromethoxy reagent, preparation

Cite this article

Wei Zheng, Fengxue Liu, Hongqiong Zhao, Ying Xu, Ning Chen, Yingjie Liu. Recent Progress on Methods for the Preparation of Mono/Di/Trifluoromethoxylation Reagents[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3321-3334.

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Fig. & Tab. 29

Scheme 1. Synthesis of O-[11C] methyl-l-tyrosine and O-[18F] fluoromethyl-l-tyrosine

Scheme 2. Synthesis of 1-(fluoromethoxy)-3-methylbenzotriazole (FMBT)

Scheme 3. Synthesis of N-(fluoromethoxy) benzotriazole

Scheme 4. Synthesis and application of 2,6-dichloro-(difluoro- methoxy) aniline

Scheme 5. Synthesis and application of difluoromethoxy reagent 32

Scheme 6. TEMPO? catalyzed C—H difluoro/trifluoromethoxylation of (hetero) aromatic hydrocarbons

Scheme 7. Synthesis and application of N-(difluoromethoxy) pyridine salt

Scheme 8. Nucleophilic trifluoromethoxylation reactions and obtainable trifluoro methoxide anion sources

Scheme 9. Preparation of early trifluoromethoxy reagents

Scheme 10. Preparation of radical reagents N-(trifluorometh- oxy)phthalimide and its derivative

Scheme 11. Preparation and application of PhthOCF3

Scheme 12. Preparation of N-trifluoromethoxy pyridinium salt reagent 79

Scheme 13. Preparation and application of reagent 81

Scheme 14. Preparation and application of 1-OCF3 benzotriazole reagent 88

Scheme 15. Preparation and application of TAS OCF3

Scheme 16. Preparation and application of (Aryl-BIAN)- AgOCF3

Scheme 17. Preparation and application of trifluoromethylaryl sulfonate reagent 108

Scheme 18. Synthesis and application of (E)-O-trifluoromethyl benzaldehydeoxime

Scheme 19. Preparation and application of α-bromobenzyl trifluoromethyl ether (116)

Scheme 20. Preparation and application of [Ag(bpy)(PPhtBu2)(OCF3)] (125)

Scheme 21. Preparation and application of trifluoromethyl trifluoroate (130)

Scheme 22. Preparation and application of trifluoromethyl benzoate(TFBz) (151)

Scheme 23. Preparation and application of AgOCF3

Scheme 24. Preparation and application of PyOCF3

Scheme 25. Preparation and application of trifluoromethyl perfluorobutane sulfonic acid (TFNF)

Scheme 26. Preparation and application of trifluoromethoxyallyl carbonate

Scheme 27. Preparation and application of reagent N,N-dime- thylpyrrolium trifluoromethoxy 189

Scheme 28. Preparation and application of reagent 195

Scheme 29. Preparation and application of reagent [Ag(PPh- tBu2)(OCF3)]

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