Carbon-fluorine bond formation

Current Opinion in Drug Discovery and Development

Volumn 11, Issue 6, 2008, Pages 803-819

  Furuya, T ^a   Kuttruff, C A ^a   Ritter, T ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

Carbon fluorine bond formation; Electrophilic fluorination; Enantioselective fluorination; Fluorinating reagents; Fluorination; Nucleophilic fluorination

Indexed keywords

CARBON; FLUORINE;

CHEMICAL ANALYSIS; CHEMICAL BINDING; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOSELECTIVITY; FLUORINATION; REVIEW;

CARBON; HALOGENATION; STEREOISOMERISM;

EID: 54549103372     PISSN: 13676733     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Review

References (116)

1. Böhm HJ, Banner D, Bendels S, Kansy M, Kuhn B, Müller K, Obst-Sander U, Stahl M: Fluorine in medicinal chemistry. ChemBioChem (2004) 5(5):637-643.
2. Müller K, Faeh C, Diederich F: Fluorine in pharmaceuticals: Looking beyond intuition. Science (2007) 317(5846):1881-1886.
3. Purser S, Moore PR, Swallow S, Gouverneur V: Fluorine in medicinal chemistry. Chem Soc Rev (2008) 37(2):320-330.
4. Jeschke P: The unique role of fluorine in the design of active ingredients for modern crop protection. ChemBioChem (2004) 5(5):571-589.
5. Phelps ME: Positron emission tomography provides molecular imaging of biological processes. Proc Natl Acad Sci USA (2000) 97(16):9226-9233.
6. Ametamey SM, Honer M, Schubiger PA: Molecular imaging with PET. Chem Rev (2008) 108(5):1501-1516.
7. Hung MH, Farnham WB, Feiring AE, Rozen S: Functional fluoromonomers and fluoropolymers. In: Fluoropolymers. Hougham G, Cassidy PE, Johns K, Davidson T (Eds), Plenum Publishing Co, New York, NY, USA (1999).
8. Wei HC, Lagow RJ: The synthesis of the largest perfluoro macrocycles; perfluoro [60]-crown-20 and perfluoro [30]-crown-10. Chem Commun (2000) (21):2139-2141.
9. O'Hagan D: Understanding organofluorine chemistry. An introduction to the C-F bond. Chem Soc Rev (2008) 37(2):308-319.
10. Smart BE: Fluorine substituent effects (on bioactivity). J Fluorine Chem (2001) 109(1):3-11.
11. Bondi A: van der Waals volumes and radii. J Phys Chem (1964) 68(3):441-451.
12. Hudlicky M, Pavlath AE (Eds): Chemistry of Organic Fluorine Compounds II. American Chemical Society, Washington, DC, USA (1995).
13. 2A receptor antagonists. J Med Chem (2001) 44(10):1603-1614.
14. Berkowitz DB, Bose M: (α-Monofluoroalkyl)phosphonates: A class of isoacidic and 'tunable' mimics of biological phosphates. J Fluorine Chem (2001) 112(1):13-33.
15. Tanake F, Fukuse H, Wada H, Fukushima M: The history, mechanism and clinical use of oral 5-fluorouracil derivative chemotherapeutic agents. Curr Pharm Biotechnol (2000) 1(2):137-164.
16. Couturier O, Luxen A, Chatal JF, Vuillez JP, Rigo P, Hustinx R: Fluorinated tracers for imaging cancer with positron emission tomography. Eur J Nucl Med Mol Imaging (2004) 31(8):1182-1206.
17. Kirk KL: Fluorination in medicinal chemistry: Methods, strategies, and recent developments. Org Process Res Dev (2008) 12(2):305- 321.
18. Gribble GW: Natural organohalogens: A new frontier for medicinal agents? J Chem Ed (2004) 81(10):1441-1449.
19. Chambers RD (Ed): Fluorine in Organic Chemistry. Blackwell Publishing Ltd, Oxford, UK (2004).
20. Kirsch P (Ed): Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications. Wiley-VCH Verlag GmbH & Co KGaA, Weinheim, Germany (2004).
21. Uneyama K (Ed): Organofluorine Chemistry. Blackwell Publishing Ltd, Oxford, UK (2006).
22. Brunet VA, O'Hagan D: Catalytic asymmetric fluorination comes of age. Angew Chem Int Ed (2008) 47(7):1179-1182.
23. Emsley J: Very strong hydrogen bonds. Chem Soc Rev (1980) 9(1):91-124.
24. Manna S, Falck JR, Mioskowski C: A convenient preparation of alkyl halides and cyanides from alcohols by modification of the Mitsunobu procedure. Synth Commun (1985) 15(8):663-668.
25. Tullock CW, Coffman DD: Synthesis of fluorides by metathesis with sodium fluoride. J Org Chem (1960) 25(11):2016-2019.
26. Shahak I, Bergmann ED: Organic fluorine compounds. Part XXXVI. Preparation of N-substituted amides of α- fluoroacids. J Chem Soc C (1967):319-320.
27. 2 groups by -F. J Am Chem Soc (1956) 78(23):6034-6037.
28. Bram G, Loupy A, Pigeon P: Easy and efficient heterogeneous nucleophilic fluorination without solvent. Synth Commun (1988) 18(14):1661-1668.
29. Collona S, Re A, Gelbard G, Cesarotti E: Anionic activation in polymer supported reactions. Part 2. Stereochemical studies on the introduction of fluorine at chiral centers and in biologically significant molecules. J Chem Soc, Perkin Trans 1 (1979):2248-2252.
30. Ishikawa N, Kitazume T, Yamazaki T, Mochida Y, Tatsumo T: Enhanced effect of spray-dried potassium fluoride on fluorination. Chem Lett (1981) 10(6):761-764.
31. Clark JH, Hyde A, Smith DK: Calcium fluoride-supported alkali metal fluorides. New reagents for nucleophilic fluorine transfer reactions. J Chem Soc, Chem Commun (1986) (10):791-793.
32. Liotta CL, Harris HP: Chemistry of naked anions. I. Reactions of the 18-crown-6 complex of potassium fluoride with organic substrates in aprotic organic solvents. J Am Chem Soc (1974) 96(7):2250-2252.
33. 4PBr/18-crown-6 reagent system. Chem Lett (1988) 17(8):1355-1358.
34. Sharma RK, Fry JL: Instability of anhydrous tetra-n-alkylammonium fluorides. J Org Chem (1983) 48(12):2112-2114.
35. Christe KO, Wilson WW, Wilson RD, Bau R, Feng JA: Syntheses, properties, and structures of anhydrous tetramethylammonium fluoride and its 1:1 adduct with trans-3-amino-2-butenenitrile. J Am Chem Soc (1990) 112(21):7619-7625.
36. Sun H, DiMagno SG: Anhydrous tetrabutylammonium fluoride. J Am Chem Soc (2005) 127(7):2050-2051.
37. Sun H, DiMagno SG: Room-temperature nucleophilic aromatic fluorination: Experimental and theoretical studies. Angew Chem Int Ed (2006) 45(17):2720-2725. • Demonstrates that nucleophilic aromatic substitution is feasible at significantly lower temperatures than previously observed when anhydrous fluoride is used.
38. Middleton WJ: New fluorinating reagents. Dialkylaminosulfur fluorides. J Org Chem (1975) 40(5):574-578.
39. Lal GS, Pez GP, Pesaresi RJ, Prozonic FM, Cheng H: Bis(2-methoxyethyl) aminosulfur trifluoride: A new broad-spectrum deoxofluorinating agent with enhanced thermal stability. J Org Chem (1999) 64(19):7048- 7054.
40. Umemoto T, Fukami S, Tomizawa G, Harasawa K, Kawada K, Tomita K: Power- and structure-variable fluorinating agents. The N-fluoropyridinium salt system. J Am Chem Soc (1990) 112(23):8563-8575.
41. Shimada Y, Taniguchi N, Matsuhisa A, Sakamoto K, Yatsu T, Tanaka A: Highly potent and orally active non-peptide arginine vasopressin antagonists for both V1A and V2 receptors: Synthesis and pharmacological properties of 4′-[(4,4-difluoro-5-methylidene-2,3,4,5-tetrahydro-1H-1- benzoazepin-1-yl) carbonyl]-2-phenylbenzanilide derivatives. Chem Pharm Bull (2000) 48(11):1644-1651.
42. Barnette WE: N-Fluoro-N-alkylsulfonamides: Useful reagents for the fluorination of carbanions. J Am Chem Soc (1984) 106(2):452-454.
43. Singh S, DesMarteau DD, Zuberi SS, Witz M, Huang HN: N-Fluoroperfluoroalkylsulfonimides. Remarkable new fluorination reagents. J Am Chem Soc (1987) 109(23):7194-7196.
44. Differding E, Ofner H: N-Fluorobenzenesulfonimide: A practical reagent for electrophilic fluorinations. Synlett (1991) 109(23):187-189.
45. Differding E, Lang RW: New fluorinating reagents - I. The first enantioselective fluorination reaction. Tetrahedron Lett (1988) 29(47):6087-6090.
46. 4 in action: Tamed fluorine at your service. J Fluorine Chem (1998) 87(1):1-17.
47. Gilicinski AG, Pez GP, Syvret RG, Lal GS: On the relative power of electrophilic fluorinating reagents of the N-F class. J Fluorine Chem (1992) 59(1):157-162.
48. Clark JH: Fluoride ion as a base in organic synthesis. Chem Rev (1980) 80(5):429-452.
49. Kim DW, Song CE, Chi DY: New method of fluorination using potassium fluoride in ionic liquid: Significantly enhanced reactivity of fluoride and improved selectivity. J Am Chem Soc (2002) 124(35):10278- 10279.
50. Howard JAK, Hoy VJ, O'Hagan D, Smith GT: How good is fluorine as a hydrogen bond acceptor? Tetrahedron (1996) 52(38):12613-12622.
51. N2 reactions catalyzed by protic solvents: Facile fluorination for isotopic labeling of diagnostic molecules. J Am Chem Soc (2006) 128(50):16394-16397.
52. Kim DW, Jeong HJ, Lim ST, Sohn MH, Katzenellenbogen JA, Chi DY: Facile nucleophilic fluorination reactions using tert-alcohols as reaction medium: Significantly enhanced reactivity of alkali metal fluorides and improved selectivity. J Org Chem (2008) 73(3):957-962. • Describes the use of tert-butyl alcohol as a solvent for nucleophilic fluorination. Tert-butyl alcohol reduces the basicity of fluoride and therefore the potential for side reactions.
53. 18F] N-3-fluoropropyl-2-β-carbomethoxy-3-β-(4-iodophenyl) nortropane and the first human study with positron emission tomography. Nucl Med Biol (1996) 23(8):999-1004.
54. Shinde SS, Lee BS, Chi DY: Synergistic effect of two solvents, tert-alcohol and ionic liquid, in one molecule in nucleophilic fluorination. Org Lett (2008) 10(5):733-735.
55. Pilcher AS, Ammon HL, DeShong P: Utilization of tetrabutyl-ammonium triphenylsilyldifluoride as a fluoride source for nucleophilic fluorination. J Am Chem Soc (1995) 117(18):5166-5167.
56. Hamatani T, Matsubara S, Matsuda H, Schlosser M: A stereocontrolled access to vicinal difluoroalkenes. Tetrahedron (1988) 44(10):2875-2881.
57. Hunter L, O'Hagan D, Slawin AMZ: Enantioselective synthesis of an all-syn four vicinal fluorine motif. J Am Chem Soc (2006) 128(51):16422-16423.
58. Tozer MJ, Herpin TF: Methods for the synthesis of gem-difluoromethylene compounds. Tetrahedron (1996) 52(26):8619-8683.
59. Lal GS, Pez GP, Pesaresi RJ, Prozonic FM: Bis(2-methoxyethyl) aminosulfur trifluoride: A new broad-spectrum deoxofluorinating agent with enhanced thermal stability. Chem Commun (1999) (2):215-216.
60. Dolensky B, Kirk KL: Preparation of (fluoromethyl)- and (difluoromethyl)imidazoles. Collect Czech Chem Commun (2002) 67(9):1335-1344.
61. O'Hagan D, Schaffrath C, Cobb SL, Hamilton JTG, Murphy CD: Biosynthesis of an organofluorine molecule. Nature (2002) 416(6878):279.
62. Deng H, O'Hagan D, Schaffrath C: Fluorometabolite biosynthesis and the fluorinase from Streptomyces cattleya. Nat Prod Rep (2004) 21(6):773-784.
63. O'Hagan D: Recent developments on the fluorinase from Streptomyces cattleya. J Fluorine Chem (2006) 127(11):1479-1483.
64. Fujimori DG, Walsh CT: What's new in enzymatic halogenations. Curr Opin Chem Biol (2007) 11(5):553-560.
65. 18F bond formation, an enzymatic tool for PET labelling. Chem Commun (2006) (6):652-654.
66. Adams DJ, Clark JH: Nucleophilic routes to selectively fluorinated aromatics. Chem Soc Rev (1999) 28(4):225-231.
67. Horwitz JP, Tomson AJ: Some 6-substituted uracils. J Org Chem (1961) 26(9):3392-3395.
68. Kiburis J, Lister JH: Syntheses of 6-fluoropurine and 6-fluoropurine-9-β-D-ribofuranoside. J Chem Soc D (1969) (8):381a.
69. Barlin GB, Young AC: Useful preparations involving the reactions of nucleophiles with some trimethylammonioderivatives of nitrogen heterocycles. J Chem Soc, Perkin Trans 1 (1972) (21):1269-1272.
70. 18]fluoroarenes. J Chem Soc, Chem Commun (1995) (21):2215-2216.
71. 18F] fluoride ion with diaryliodonium salts. J Chem Soc, Perkin Trans 1 (1998) (13):2043-2046.
72. 18F] fluorobenzene. J Labelled Comp Radiopharm (2004) 47(7):429- 441.
73. Adams DJ, Clark JH, McFarland H: The formation of 4,4′- difluorobenzophenone from 4,4′-dinitrodiphenylmethane. J Fluorine Chem (1998) 92(2):127-129.
74. Zhdankin VV: Recent developments in the chemistry of polyvalent iodine compounds. Chem Rev (2002) 102(7):1179-1182.
75. Beringer FM, Brierley A, Drexler M, Gindler EM, Lumpkin CC: Diaryliodonium salts. II. The phenylation of organic and inorganic bases. J Am Chem Soc (1953) 75(11):2708-2712.
76. 18F-labeled aryl fluorides. J Fluorine Chem (1985) 27(2):177-191.
77. 18F] fluoride. J Am Chem Soc (2007) 129(25):8018-8025.
78. Lam YH, Bobbio C, Cooper IR, Gouverneur V: A concise synthesis of enantioenriched fluorinated carbocycles. Angew Chemie International Ed (2007) 46(27):5106-5110.
79. Davis FA, Zhou P, Murphy CK, Sundarababu G, Qi H, Han W, Przeslawski RM, Chen BC, Carroll PJ: Asymmetric fluorination of enolates with nonracemic N-fluoro-2,10-camphorsultams. J Org Chem (1998) 63(7):2273-2280.
80. Shibata N, Suzuki E, Takeuchi Y: A fundamentally new approach to enantioselective fluorination based on cinchona alkaloid derivatives/Selectfluor combination. J Am Chem Soc (2000) 122(43):10728-10729.
81. Ishimaru T, Shibata N, Horikawa T, Yasuda N, Nakamura S, Toru T, Shiro M: Cinchona alkaloid catalyzed enantioselective fluorination of allyl silanes, silyl enol ethers, and oxindoles. Angew Chem Int Ed (2008) 47(22):4157-4161. • Describes the enantioselective fluorination of nucleophiles using a substoichiometric amount of chiral amine.
82. E2′ fluorination of allenylsilanes: Synthesis of enantioenriched propargylic fluorides. Org Biomol Chem (2008) 6(10):1731-1733.
83. Grée D, Grée R: A new strategy for the synthesis of optically active benzylic fluorides and corresponding five-membered heteroaromatic analogues. Tetrahedron Lett (2007) 48(31):5435-5438.
84. Frantz DE, Fässler, R, Carreira EM: Facile enantioselective synthesis of propargylic alcohols by direct addition of terminal alkynes to aldehydes. J Am Chem Soc (2000) 122(8):1806-1807.
85. Anand NK, Carreira EM: A simple, mild catalytic, enantioselective addition of terminal acetylenes to aldehydes. J Am Chem Soc (2001) 123(39):9687-9688.
86. 18F]-N-fluorobenzenesulfonimide. Chem Commun (2007) (23):2330-2332.
87. Beeson TD, MacMillan DWC: Enantioselective organocatalytic α-fluorination of aldehydes. J Am Chem Soc (2005) 127(24):8826-8828. • This paper and references [88] and [89] describe the enantioselective organocatalytic α-fluorination of aldehydes.
88. Marigo M, Fielenbach D, Braunton A, Kjærsgaard A, Jørgensen KA: Enantioselective formation of stereogenic carbon-fluorine centers by a simple catalytic method. Angew Chem Int Ed (2005) 44(24):3703-3706. • This paper and references [87] and [89] describe the enantioselective organocatalytic α-fluorination of aldehydes.
89. Steiner DD, Mase N, Barbas CF III: Direct asymmetric α-fluorination of aldehydes. Angew Chem Int Ed (2005) 44(24):3706-3710. • This paper and references [87] and [88] describe the enantioselective organocatalytic α-fluorination of aldehydes.
90. Enders D, Hüttl MRM: Direct organocatalytic α-fluorination of aldehydes and ketones. Synlett (2005) (6):991-993.
91. Hintermann L, Togni A: Catalytic enantioselective fluorination of β-ketoesters. Angew Chem Int Ed (2000) 39(23):4359- 4362. • Describes the first transition metal-catalyzed enantioselective electrophilic fluorination of carbonyl compounds.
92. Pihko PM: Enantioselective α-fluorination of carbonyl compounds: Organocatalysis or metal catalysis? Angew Chem Int Ed (2006) 45(4):544-547.
93. Hamashima Y, Yagi K, Takano H, Tamás L, Sodeoka M: An efficient enantioselective fluorination of various β-ketoesters catalyzed by chiral palladium complexes. J Am Chem Soc (2002) 124(49): 14530-14531.
94. Ma JA, Cahard D: Copper(II) triflate-bis(oxazoline)-catalysed enantioselective electrophilic fluorination of β-ketoesters. Tetrahedron Asymmetry (2004) 15(6):1007-1011.
95. Shibata N, Ishimaru T, Nagai T, Kohno J, Toru T: First enantio-flexible fluorination reaction using metal-bis(oxazoline) complexes. Synlett (2004) (10):1703-1706.
96. Hewawasam P, Gribkoff VK, Pendri Y, Dworetzky SI, Meanwell NA, Martinez E, Boissard CG, Post-Munson DJ, Trojnacki JT, Yeleswaram K, Pajor LM et al: The synthesis and characterization of BMS-204352 (MaxiPost™) and related 3-fluorooxindoles as openers of maxi-K potassium channels. Bioorg Med Chem Lett (2002) 12(7):1023-1026.
97. Hamashima Y, Suzuki T, Takano H, Shimura Y, Sodeoka M: Catalytic enantioselective fluorination of oxindoles. J Am Chem Soc (2005) 127(29):10164-10165.
98. Shibata N, Kohno J, Takai K, Shimaru T, Nakmura S, Toru T, Kanemasa S: Highly enantioselective catalytic fluorination and chlorination reactions of carbonyl compounds capable of two-point binding. Angew Chem Int Ed (2005) 44(27):4204-4207.
99. Adachi K, Ohira Y, Tomizawa G, Ishihara S, Oishi S: Electrophilic fluorination with N,N′-difluoro-2,2′-bipyridinium salt and elemental fluorine. J Fluorine Chem (2003) 120(2):173-183.
100. Davis FA, Han W, Murphy CK: Selective, electrophilic fluorinations using N-fluoro-o-benzenedisulfonimide. J Org Chem (1995) 60(15):4730-4737.
101. Bryce MR, Chambers RD, Mullins ST, Parkin A: Electrophilic fluorination of arylatrialkultin derivatives with caesium fluoroxysulphate. J Chem Soc, Chem Commun (1986) (21):1623-1624.
102. Tius MA, Kawakami JK: Vinyl fluorides from vinylstannanes. Synth Commun (1992) 22(10):1461-1471.
103. Stacey M, Tatlow JC, Sharpe AG (Ed): Advances in Fluorine Chemistry. Academic Press, New York, NY, USA (1960).
104. Banks RE, Tatlow JC: A guide to modern organofluorine chemistry. J Fluorine Chem (1986) 33(1-4):227-346.
105. Bailey J, Plevey RG, Tatlow JC: Fluorinations with potassium tetrafluorocobaltate[III]. Part VIIII. Fluorinations of toluene and of phenylacetic acid. J Fluorine Chem (1988) 39(1):23-37.
106. Subramanian MA, Manzer LE: A 'greener' synthetic route for fluoroaromatics via copper(II) fluoride. Science (2002) 297(5587):1665.
107. Janmanchi KM, Dolbier WR Jr: Highly reactive and regenerable fluorinating agent for oxidative fluorination of aromatics. Org Process Res Dev (2008) 12(2):349-354.
108. Grushin VV: Palladium fluoride complexes: One more step toward metal-mediated C-F bond formation. Chem Eur J (2002) 8(5):1006-1014.
109. Yandulov DV, Tran NT: Aryl-fluoride reductive elimination from Pd(II): Feasibility assessment from theory and experiment. J Am Chem Soc (2007) 129(5):1342-1358.
110. Grushin VV, Marshall WJ: Ar-F reductive elimination from palladium(II) revisited. Organometallics (2007) 26(20):4997-5002.
111. Hull KL, Anani WQ, Sanford MS: Palladium-catalyzed fluorination of carbon-hydrogen bonds. J Am Chem Soc (2006) 128(22):7134-7135. • Describes the first palladium-catalyzed fluorination of an arene.
112. Kaspi AW, Yahav-Levi A, Goldberg I, Vigalok A: Xenon difluoride induced aryl iodide reductive elimination: A simple access to difluoropalladium(II) complexes. Inorg Chem (2008) 47(1):5-7.
113. Furuya T, Kaiser HM, Ritter T: Palladium-mediated fluorination of arylboronic acids. Angew Chem Int Ed (2008) 47(32):5993-5996. • Describes a general fluorination of boronic acids via stoichiometric palladium complexes.
114. Furuya T, Ritter T: Carbon-fluorine reductive elimination from a high-valent palladium fluoride. J Am Chem Soc (2008) 130(31):10060-10061.
115. ASAHI GLASS CO (Kumai S, Seki T, Wada A): Preparation of fluorinated pyridines. JP-04164068 (1992).
116. EI DUPONT DE NEMOURS & CO (Grushin V): Processes for preparing fluoroarenes from haloarenes. US-07202388 (2007).