Introduction
Fluorine is one of the vital organic chemistry elements, which can lead to significant variations in molecules’ chemical and physical properties. Thus, organofluorine compounds have been widely used in functional materials, medicinal science, life science, and many other fields [375,376,377,4]. In contrast to the abundance of inorganic fluorine-containing compounds, naturally occurring organofluorine compounds are scarce. Therefore, many efforts have been taken to develop fluorine-incorporation methods into organic molecules [5]. Among them, deoxofluorination of alcohols via nucleophilic fluorination is one of the major methods to acquire alkyl fluorides (Fig. 1). After SF4 was successfully applied in deoxofluorination in 1958 [7], many deoxofluorination reagents have been invented [379,380,381,382,383,384,385,386,387,388,389,390,17]. At present, the widely used reagents can be divided into three categories: 1) sulfur fluorides and their derivatives (SF reagents, Fig. 1a)...
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Kirsch, P (Wiley-VCH, 2013) In Modern Fluoroorganic Chemistry: Synthesis, Reactivity Applications 2nd edn
Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J (2011) Organic fluorine compounds: a great opportunity for enhanced materials properties. Chem Soc Rev 40: 3496–3508
Purser S, Moore PR, Swallow S, Gouverneur V (2008) Fluorine in medicinal chemistry. Chem Soc Rev 37: 320–330
Fujiwara T, O’Hagan D (2014) Successful fluorine containing herbicide agrochemicals. J Fluorine Chem 167: 16–29
Liang T, Neumann CN, Ritter, T (2013) Introduction of Fluorine and Fluorine-Containing Functional Groups. Angew Chem Int Ed 52: 8214–8264
Ayi AI, Remit M. Guedj R (1981) Monofluoration stereoselective par le phenyltetrafluorophosphorane (PhPF4) Part. II. Application a la synthese des isomeres thréo et érythro des alkyl-2 fluoro-3 phenylpropanoates de methyle. Analyse conformationnelle par R.M.N. de 19F et 1H. J Fluorine Chem 17: 127–143
Smith, WC, Tullock, CW, Muetterties, EL, Hasek, WR, Fawcett, FS, Exgelhardt, V A, Coffman, DD (1959) Fluorination reactions of sulfur tetrafluoride. J Am Chem Soc 81: 3165–3166
Middleton, W. J (1975) New fluorinating reagents. Dialkylaminosulfur fluorides. J Org Chem 40: 574–578
Lal G. S, Pez G. P, Pesaresi R. J, Prozonic F. M, Cheng H (1999) Bis(2-methoxyethyl)aminosulfur trifluoride: a new broad-spectrum deoxofluorinating agent with enhanced thermal stability. J Org Chem 64: 7048–7054
Beaulieu F, Beauregard LP, Courchesne G, Couturier M, LaFlamme F, L'Heureux, A (2009) Aminodifluorosulfinium tetrafluoroborate salts as stable and crystalline deoxofluorinating reagents. Org Lett 11: 5050–5053
Umemoto T, Singh RP, Xu Y, Saito N (2010) Discovery of 4-tert-butyl-2, 6-dimethylphenylsulfur trifluoride as a deoxofluorinating agent with high thermal stability as well as unusual resistance to aqueous hydrolysis, and its diverse fluorination capabilities including deoxofluoro-arylsulfinylation with high stereoselectivity. J Am Chem Soc 132: 18199–18205
Nielsen M. K, Ugaz C. R, Li W, Doyle A. G (2015) PyFluor: a low-cost, stable, and selective deoxyfluorination reagent. J Am Chem Soc 137: 9571–9574
Ishikawa N, Iwakiri H, Takaoka A (1979) F-propene-dialkylamine reaction products as fluorinating agents. Bull Chem Soc Jpn 52: 3377–3380
Bellavance G, Dube´ P, Nguyen B (2012) Tetramethylfluoroformamidinium hexafluorophosphate (TFFH) as a mild deoxofluorination reagent. Synlett 23: 569–572
Sladojevich F, Arlow S.I, Tang P, Ritter T (2013) Late-stage deoxyfluorination of alcohols with PhenoFluor. J Am Chem Soc 135: 2470–2473
Goldberg NW, Shen X, Li J, Ritter T (2016) AlkylFluor: Deoxyfluorination of Alcohols. Org Lett 18: 6102–6104
Li L, Ni C, Fei W, Hu J (2016). Deoxyfluorination of alcohols with 3,3-difluoro-1,2-diarylcyclopropenes. Nature Comm 7: 13320
Li L, Wang F, Ni C, Hu J (2013) Synthesis of gem-Difluorocyclopropa(e)nes and O-, S-, N-, and P-Difluoromethylated Compounds with TMSCF2Br. Angew Chem Int Ed 52: 12390–12394
Wang F, Luo T, Hu J, Wang Y, Krishnan HS, Jog PV, Ganesh SK, Prakash GKS, Olah GA (2011) Synthesis of gem-Difluorinated Cyclopropanes and Cyclopropenes: Trifluoromethyltrimethylsilane as a Difluorocarbene Source. Angew Chem Int Ed 50: 7153–7157
Eujien R, Hoge B (1995) Donor-free bis(trifluoromethyl)cadmium, (CF3)2Cd: a readily available low-temperature difluorocarbene source. J Organomet Chem 503: C51-C54
Dolbier Jr W. R, Battiste M. A (2003) Structure, synthesis, and chemical reactions of fluorinated cyclopropanes and cyclopropenes. Chem Rev 103: 1071–1098
Ni C, Hu J (2014) Recent advances in the synthetic application of difluorocarbene. Synthesis 46, 842–863
Bessard Y, Schlosser M (1991) gem-Difluorocyclopropenes by [1+2]cycloaddition reactions between difluorocarbene and acetylenes having terminal or internal triple bonds. Tetrahedron 47: 7323–7328
Xu W, Chen QY (2002) 3,3-Difluoro-1-iodocyclopropenes: a simple synthesis and their reactions. J Org Chem 67: 9421–9427
Cheng ZL, Chen QY (2005) Difluorocarbene chemistry: synthesis of gem-difluorocyclopropenylalkynes and 3,3,3’,3’-tetrafluorobicyclopropyl-1,10-dienes. J Fluorine Chem 126: 39–43
Kelly B. D, Lambert T. H (2009) Aromatic cation activation of alcohols: conversion to alkyl chlorides using dichlorodiphenylcyclopropene. J Am Chem Soc 131: 13930–13931
Vanos C. M. Lambert T. H (2011) Development of a catalytic platform for nucleophilic substitution: cyclopropenone-catalyzed chlorodehydration of alcohols. Angew Chem Int Ed 50: 12222–12226
Umemoto T, Singh R. P, Xu Y, Saito N (2010) Discovery of 4-tert-butyl-2, 6-dimethylphenylsulfur trifluoride as a deoxofluorinating agent with high thermal stability as well as unusual resistance to aqueous hydrolysis, and its diverse fluorination capabilities including deoxofluoro-arylsulfinylation with high stereoselectivity. J Am Chem Soc 132: 18199–18205
Nielsen MK, Ugaz CR, Li W, Doyle AG (2015) PyFluor: a low-cost, stable, and selective deoxyfluorination reagent. J Am Chem Soc 137: 9571–9574
Nakamura M, Isobe H, Nakamura E (2003) Cyclopropenone acetals: synthesis and reactions. Chem Rev 103: 1295–1326
Boger DL, Brotherton CE (1986) Thermal reactions of cyclopropenone ketals. Key mechanistic features and scope of the cycloaddition reactions of delocalized singlet vinylcarbenes: three-carbon 1,1-/1,3-dipoles. J Am Chem Soc 108: 6695–6713
Tokuyama H, Isaka M, Nakamura E (1992) Thermal reactions of substituted cyclopropenone acetals. Regio- and stereochemistry of vinylcarbene formation and low-temperature [3+2] cycloaddition. J Am Chem Soc 114: 5523–5530
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2020 Springer Nature Singapore Pte Ltd.
About this entry
Cite this entry
Zhang, W., Shen, X. (2020). CpFluor Deoxofluorination. In: Hu, J., Umemoto, T. (eds) Fluorination. Synthetic Organofluorine Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-3896-9_44
Download citation
DOI: https://doi.org/10.1007/978-981-10-3896-9_44
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-3895-2
Online ISBN: 978-981-10-3896-9
eBook Packages: Chemistry and Materials ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics