Subscribe to RSS
DOI: 10.1055/s-2002-35626
Recent Advances in Nucleophilic Fluorination Reactions of Organic Compounds Using Deoxofluor and DAST
Publication History
Publication Date:
20 November 2002 (online)
![](https://www.thieme-connect.de/media/synthesis/200217/lookinside/thumbnails/10.1055-s-2002-35626-1.jpg)
Abstract
Selective fluorination of organic compounds continues to be a stimulating and exciting area of research. While a variety of fluorinating reagents and methodologies have been developed to fulfill the increasing demand for site selective fluorination of organic compounds, applications of Deoxofluor and DAST continue to be used widely. Our interest in applying synthetic methods for introducing fluorine or a fluorinated group into a large variety of organic compounds encouraged this review which highlights recent progress in fluorination reactions using Deoxofluor [bis(2-methoxyethyl)aminosulfur trifluoride] and DAST (diethylaminosulfur trifluoride) as key nucleophilic fluorinating reagents. This review covers the literature for fluorination reactions of organic compounds using Deoxofluor and DAST from January 1999 through July 2002.
-
1 Introduction
-
2 Synthesis of Deoxofluor [Bis(2-methoxyethyl)aminosulfur Trifluoride] and DAST (Diethylaminosulfur Trifluoride)
-
3 Fluorination Reactions with Deoxofluor and DAST
-
3.1 Alcohols, Amino Alcohols, and Diols
-
3.2 Carbohydrates
-
3.3 Aldehydes and Ketones
-
3.4 Dicarbonyls
-
3.5 Sulfides, Sulfoxides, Thioesters and Thiocarbonyls
-
3.6 Carboxylic Acids and Acid Chlorides
-
3.7 Glyoxal Hydrates and Anhydrous Glyoxals
-
3.8 Epoxides (Oxiranes)
-
3.9 Peptides
-
3.10 Ketoximes
-
4 Miscellaneous Reactions
-
4.1 Synthesis of Functionalized Oxazolines and Oxazoles
-
4.2 Synthesis of Amides from Carboxylic Acids
-
4.3 Synthesis of Cholest-5-ene-3β,4β-diyl Diacetate (Steroid)
-
4.4 Cycloetherization
-
5 Reaction Mechanisms Using Deoxofluor and DAST
-
5.1 Alcohols
-
5.2 Aldehydes and Ketones
-
5.3 Carboxylic Acids
-
5.4 Sulfoxides
-
5.5 Glyoxal Hydrates
-
5.6 Ketoximes
-
6 Conclusions
Key words
Deoxofluor - DAST - nucleophilic reactions - fluorination - halogenation
- 1 For the ability of fluorine to
change the properties of organic molecules, see:
Smart BE. Characteristics of C-F systems, In Organofluorine Chemistry: Principles and Commercial ApplicationsBanks RE.Smart BE.Tatlow JC. Plenum; New York: 1994. p.57 - For the use of organofluorine compounds in medicinal and biomedical chemistry, see:
-
2a
Biomedical
Frontiers of Fluorine Chemistry
Ojima I.McCarthy JR.Welch JT. American Chemical Society; Washington DC: 1996. ; ACS Symposium Series 639: -
2b
Organic
Chemistry in Medicinal Chemistry and Biomedical Applications
Filler R. Elsevier; Amsterdam: 1993. -
2c
Welch JT.Eswaraksrishnan S. Fluorine in Bioorganic Chemistry Wiley; New York: 1991. -
2d
Filler R.Kirk K. Biological Properties of Fluorinated Compounds, In Chemistry of Organic Fluorine Compounds II: A Critical ReviewHudlicky M.Pavlath AE. American Chemical Society; Washington DC: 1995. ACS Monograph 187: 1011 -
2e
Elliot AJ. Fluorinated Pharmaceuticals, In Chemistry of Organic Fluorine Compounds II: A Critical ReviewHudlicky M.Pavlath AE. American Chemical Society; Washington DC: 1995. ACS Monograph 187: 1119-1125 -
2f
Enantiocontrolled
Synthesis of Organofluorine Compounds, Stereochemical Challenge
and Biomedical Targets
Sholoshonok VA. Wiley: New York, 1999. -
3a For
the use of organofluorine compounds in agrosciences, see:
Cartwright D. Recent Developments in Fluorine-Containing Agrochemicals, In Organofluorine Chemistry: Principles and Commercial ApplicationsBanks RE.Smart BE.Tatlow JC. Plenum; New York: 1994. p.237 -
3b
Lang RW. Fluorinated Agrochemicals, In Chemistry of Organic Fluorine Compounds IIHudlicky M.Pavlath AE. American Chemical Society; Washington DC: 1995. ; ACS Monograph 187: 1143 - 4
Demitras GC.Kent RA.MacDiarmid AG. Chem. Ind. (London) 1964, 1712 - 5
Middleton WJ. J. Org. Chem. 1975, 40: 574 -
6a
Lal GS.Pez GP.Pesaresi RJ.Prozonic FM. Chem. Commun. 1999, 215 -
6b
Lal GS.Pez GP.Pesaresi RJ.Prozonic FM.Cheng H. J. Org. Chem. 1999, 64: 7048 - 7
Singh RP.Shreeve JM. J. Fluorine Chem. 2002, 116: 23 - 8
Hallett DJ.Gerhard U.Goodacre SC.Hitzel L.Sparey TJ.Rowley TSM.Ball RG. J. Org. Chem. 2000, 65: 4984 - 9
Sutherland A.Vederas JC. Chem. Commun. 1999, 1739 - 10
De Jonghe S.Overmeire IV.Calenbergh SV.Hendrix C.Busson R.De Keukeleire D.Herdewijn P. Eur. J. Org. Chem. 2000, 3177 - 11
Huang H.Han W.Noodleman L.Grynszpan F. Bioorg. Med. Chem. 2001, 9: 3185 - 12
Taing M.Keng Y.Shen K.Wu L.Lawrence DS.Zhang Z. Biochemistry 1999, 38: 3793 - 13
Inoue M.Hiratake J.Suzuki H.Kumagai H.Sakata K. Biochemistry 2000, 39: 7764 - 14
Shabat D.Itzhaky H.Reymond J.-L.Keinan E. Nature (London) 1995, 374: 143 - 15
Ryberg P.Matsson O. J. Org. Chem. 2002, 67: 811 - 16
Grunewald GL.Caldwell TM.Li Q.Criscione KR. J. Med. Chem. 2001, 44: 2849 -
17a
Morton GO.Lancaster JE.Van Lear GE.Fulmer W.Meyer WE. J. Am. Chem. Soc. 1969, 91: 1535 -
17b
Lamberth C. Recent Res. Dev. Synth. Org. Chem. 1998, 1 - 18
Vera-Ayoso Y.Borrachero P.Cabrera-Escribano F.Diánez MJ.Estrada MD.Gómez-Guillén M.López-Castro A.Pérez-Garrido S. Tetrahedron: Asymmetry 2001, 12: 2031 - 19
Takamatsu S.Maruyama T.Katayama S.Hirose N.Naito M.Izawa K. J. Org. Chem. 2001, 66: 7469 - 20
Maruyama T.Takamatsu S.Kozai S.Satoh Y.Izawa K. Chem. Pharm. Bull. 1999, 47: 966 - 21
Albert M.Repetschnigg W.Ortner J.Gomes J.Paul BJ.Illaszewicz C.Weber H.Steiner W.Dax K. Carbohydr. Res. 2000, 326: 395 - 22
Wachtmeister J.Muhlman A.Classon B.Samuelsson B. Tetrahedron 1999, 55: 10761 -
23a
Mikhailopulo IA.Sivets GG. Helv. Chim. Acta 1999, 82: 2052 -
23b
Shortnacy-Fowler AT.Tiwari KN.Montgomery JA.Buckheit RW.Secrist JA. Helv. Chim. Acta 1999, 82: 2240 - 24
Borrachero P.Cabrera-Escribano F.Carmona AT.Goómez-Guillén M. Tetrahedron: Asymmetry 2000, 11: 2927 - 25
Wong AW.He S.Withers SG. Can. J. Chem. 2001, 79: 510 - 26
Aghmiz ML.Diaz Y.Jana GH.Matheu MI.Echarri R.Castillon S.Jimeno ML. Tetrahedron 2001, 57: 6733 - 27
Card PJ.Reddy GS. J. Org. Chem. 1983, 48: 4734 - 28
Albert M.Repetschnigg W.Ortner J.Gomes J.Paul BJ.Illaszewicz C.Weber H.Steiner W.Dax K. Carbohydr. Res. 2000, 326: 395 -
29a
Yoshimura Y.Kitano K.Endo M.Yamada K.Sakata S.Miura S.Machida H. Nucleosides Nucleotides 1999, 18: 815 -
29b
Mikhailopulo IA.Sivets GG.Khripach NB. Nucleosides Nucleotides 1999, 18: 689 - 30
Singh RP.Chakraborty D.Shreeve JM. J. Fluorine Chem. 2002, 111: 153 - 31
Ichikawa M.Ichikawa Y. Bioorg. & Med. Chem. Lett. 2001, 11: 1769 - 32
Mase T.Houpis IN.Akao A.Dorziotis I.Emerson K.Hoang T.Iida T.Itoh T.Kamei K.Kato S.Kato Y.Kawasaki M.Lang F.Lee J.Lynch J.Maligres P.Molina A.Nemoto T.Okada S.Reamer R.Song JZ.Tschaen D.Wada T.Zewge D.Volante RP.Reider PJ.Tomimoto K. J. Org. Chem. 2001, 66: 6775 - 33
Guirgis GA.Bell S.Durig JR. J. Raman Spectroscopy 2000, 31: 987 - 34
Chen G.Qi Y. Huaxue Shiji 2001, 23: 296 ; Chem. Abstr. 136: 183600g - 35
Singh RP.Majumder U.Shreeve JM. J. Org. Chem. 2001, 66: 6263 - 36
Asato AE.Liu RSH. Tetrahedron Lett. 1986, 27: 3337 -
37a
Sammes PG. Chem. Rev. 1976, 76: 113 -
37b
Hermann P. In Organosulfur ChemistryFriedlima R.Skorova AE. Pergaman; Oxford: 1981. p.51 -
37c
Jarvi ET.McCarthy JR.Mehdi JR.Matthews DP.Edwards MC.Prakash NJ.Bowlin TL.Sunkara PS.Bey PJ. J. Med. Chem. 1991, 34: 647 - 38
Ringom R.Benneche T. Acta Chim. Scand. 1999, 53: 41 - 39
Laali KK.Borodkin GI. J. Fluorine Chem. 2002, 115: 169 - 40
Lal GS.Lobach E.Evans A. J. Org. Chem. 2000, 65: 4830 - 41
Suresh Babu VV.Gopi HN.Ananda K. Indian J. Chem. 2000, 39B: 384 -
42a
Singh RP.Twamley B.Shreeve JM. J. Org. Chem. 2002, 67: 1918 -
42b
Singh RP.Shreeve JM. Org. Lett. 2001, 3: 2713 - 43
Lakshmipathi P.Gree D.Gree R. Org. Lett. 2002, 4: 451 - 44
Filmon J.Gree D.Gree R. J. Fluorine Chem. 2001, 107: 271 - 45
Agbaria K.Wohnert J.Biali SE. J. Org. Chem. 2001, 66: 7059 - 46
Zhou H.Van der Donk WA. Org. Lett. 2001, 3: 593 - 47
Kirihara M.Niimi K.Okumura M.Momose T. Chem. Pharm. Bull. 2000, 48: 220 - 48
Phillips AJ.Uto Y.Wipf P.Reno MJ.Williams DR. Org. Lett. 2000, 2: 1165 - 49
Jones G.Butler DCD.Richards CJ. Tetrahedron Lett. 2000, 41: 9351 - 50
Tunoori AR.White JM.Georg GI. Org. Lett. 2000, 2: 4091 - 51
Kennedy AR.Pitt AR.Suckling CJ.Thomas M. Acta Crystallogr. 1999, 55C: 1570 - 52
Chung S.Kwon Y.Ahn Y.Jeong T.Chang Y. Bull. Korean Chem. Soc. 2000, 21: 274 ; Chem. Abstr.132: 332690g - 53
Tewson TJ.Welch MJ. J. Org. Chem. 1978, 43: 1090 - 54
McCarthy JR.Peet NP.Le Tourneau EM.Inbasekaran M. J. Am. Chem. Soc. 1985, 107: 735