フッ素化剤，含フッ素ビルディングブロック
&含フッ素生理活性化合物
Fluorinating Reagents, Building Blocks
& Fluorinated Bioactive Compounds

　医薬・農薬などの生理活性化合物の特定位置にフッ素原子を導入することで，著しく毒性が軽減されたり，薬効が増大することがあります。これはフッ素原子のもつミミック効果とブロック効果によるもので，この成功例として5-フルオロウラシルなど多くの化合物が報告されています。
　含フッ素化合物を効率的に合成する試みは多方面で行われており，フッ素化剤を用いて特定の位置にフッ素原子を導入する方法や，含フッ素合成ブロックを用いる方法が報告されています。

　近年2-フルオロ-2-ホスホノ酢酸トリエチルは，有用な二官能性含フッ素合成ブロックとして盛んに利用されています。この化合物は塩基の存在下，カルボニル化合物との反応によりα-フルオロ-α,β-不飽和エステルを生成し，次いでアルデヒドやアルコールに還元できるため，生理活性化合物合成の前駆体として非常に有用です。
　応用例としてビタミンA誘導体1)，昆虫の性フェロモン，殺虫効力のあるピレスロイドの合成などが挙げられます。

求電子的フッ素化剤 / Electrophilic Fluorinating Reagents

求核的フッ素化剤 / Nucleophilic Fluorinating Reagents

Fits 試薬 / Fits Reagents

含フッ素合成ブロック / Fluorinated Building Blocks

含フッ素生理活性化合物 / Fluorinated Bioactive Compounds

求電子的フッ素化剤 / Electrophilic Fluorinating Reagents

D3812 D3812 F0346 F0346 F0328 F0328
F0344 F0344 F0334 F0334 F0343 F0343
F0327 F0327 F0342 F0342 F0358 F0358
F0335 F0335
D3812 1,1'-Difluoro-2,2'-bipyridinium Bis(tetrafluoroborate)
F0346 1-Fluoro-2,4,6-trimethylpyridinium Tetrafluoroborate [Fluorinating Reagent]
F0328 1-Fluoro-2,4,6-trimethylpyridinium Trifluoromethanesulfonate [Fluorinating Reagent]
F0344 1-Fluoro-2,6-dichloropyridinium Tetrafluoroborate [Fluorinating Reagent]
F0334 1-Fluoropyridinium Pyridine Heptafluorodiborate [Fluorinating Reagent]
F0343 1-Fluoropyridinium Tetrafluoroborate [Fluorinating Reagent]
F0327 1-Fluoropyridinium Trifluoromethanesulfonate [Fluorinating Reagent]
F0342 2,6-Dichloro-1-fluoropyridinium Trifluoromethanesulfonate [Fluorinating Reagent]
F0358 N-Fluoro-N'-(chloromethyl)triethylenediamine Bis(tetrafluoroborate)
F0335 N-Fluorobenzenesulfonimide [Fluorinating Reagent]
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求核的フッ素化剤 / Nucleophilic Fluorinating Reagents

D1868 D1868 D2831 D2831 B2440 B2440
M1573 M1573 P0999 P0999 T1295 T1295
T1909 T1909 T1592 T1592 T1635 T1635
T1037 T1037 T1125 T1125 T1338 T1338
T1339 T1339 T2027 T2027 T2026 T2026
T2023 T2023 T2022 T2022
D1868 (Diethylamino)sulfur Trifluoride [Fluorinating Reagent]
D2831 2,2-Difluoro-1,3-dimethylimidazolidine
B2440 Bis(2-methoxyethyl)aminosulfur Trifluoride
M1573 Morpholinosulfur Trifluoride
P0999 Pyridinium Poly(hydrogenfluoride) [Fluorinating Reagent]
T1295 Tetrabutylammonium Bifluoride
T1909 Tetrabutylammonium Difluorotriphenylsilicate
T1592 Tetrabutylammonium Difluorotriphenylstannate
T1635 Tetrabutylammonium Dihydrogen Trifluoride
T1037 Tetrabutylammonium Fluoride Hydrate [for Catalyst of acylation, silylation and cleavage of silyl ether]
T1125 Tetrabutylammonium Fluoride (1mol/L in Tetrahydrofuran) [for Catalyst of acylation, silylation and cleavage of Silyl Ether]
T1338 Tetrabutylammonium Fluoride (1mol/L in Tetrahydrofuran)
T1339 Tetrabutylammonium Fluoride (70-75% in Water)
T2027 Tetraethylammonium Fluoride Tetrahydrofluoride
T2026 Tetraethylammonium Fluoride Trihydrofluoride
T2023 Triethylamine Pentahydrofluoride
T2022 Triethylamine Trihydrofluoride
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Fits 試薬 / Fits Reagents

P1081 P1081 P1080 P1080 P1659 P1659
P1082 P1082
P1081 (Perfluoro-n-octyl)phenyliodonium Trifluoromethanesulfonate
P1080 (Perfluorohexyl)phenyliodonium Trifluoromethanesulfonate
P1659 (Perfluoroisopropyl)phenyliodonium Trifluoromethanesulfonate
P1082 (Perfluoropropyl)phenyliodonium Trifluoromethanesulfonate
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含フッ素合成ブロック / Fluorinated Building Blocks

・脂肪族化合物 / Aliphatic Compounds

F0518 F0518 D2525 D2525 D2524 D2524
T1570 T1570 T1032 T1032 T2638 T2638
T2547 T2547 T0435 T0435 M1193 M1193
T1516 T1516 T1604 T1604 T1512 T1512
B1801 B1801 B3498 B3498 C2381 C2381
C0990 C0990 C1503 C1503 F0283 F0283
D2523 D2523 D1423 D1423 E0663 E0663
D2782 D2782 E0547 E0547 T0810 T0810
B1463 B1463 B1673 B1673 C1458 C1458
C1467 C1467 D2530 D2530 D2498 D2498
F0030 F0030 T0432 T0432 F0341 F0341
H0598 H0598 T1245 T1245 C1586 C1586
F0311 F0311 C0991 C0991 F0042 F0042
F0340 F0340 T0791 T0791 T0433 T0433
F0518 (1-Fluorovinyl)methyldiphenylsilane
D2525 (R)-N-(2,2-Difluoroethylidene)-1-phenylethylamine
D2524 (S)-N-(2,2-Difluoroethylidene)-1-phenylethylamine
T1570 (Trifluoromethyl)trimethylsilane [Trifluoromethylating Reagent]
T1032 1,1,1-Trichloro-2,2,2-trifluoroethane
T2638 2,2,2-Trifluoro-N-(4-methoxyphenyl)acetimidoyl Chloride
T2547 2,2,2-Trifluoro-N-phenylacetimidoyl Chloride
T0435 2,2,2-Trifluoroethanol
M1193 2,2,2-Trifluoroethyl Methanesulfonate
T1516 2,2,2-Trifluoroethyl p-Toluenesulfonate
T1604 2,2,2-Trifluoroethyl Trifluoromethanesulfonate
T1512 2-(Trifluoromethyl)acrylic Acid
B1801 2-Bromo-3,3,3-trifluoro-1-propene (stabilized with Copper chip)
B3498 2-Bromo-4-fluorobenzaldehyde
C2381 2-Chloro-5-fluorobenzaldehyde
C0990 Chlorodifluoroacetic Acid
C1503 Chlorodifluoroacetic Anhydride
F0283 Diethyl Fluoromalonate
D2523 Difluoroacetaldehyde Ethyl Hemiacetal
D1423 Difluoroacetic Acid
E0663 Ethyl 2-Fluoropropionate
D2782 Ethyl 3-(Dimethylamino)-3-ethoxy-2,2-difluoropropionate
E0547 Ethyl 3-Ethoxy-2,2-difluoro-3-hydroxypropionate
T0810 Ethyl 4,4,4-Trifluoroacetoacetate
B1463 Ethyl Bromodifluoroacetate
B1673 Ethyl Bromofluoroacetate
C1458 Ethyl Chlorodifluoroacetate
C1467 Ethyl Chlorofluoroacetate
D2530 Ethyl Dibromofluoroacetate
D2498 Ethyl Difluoroacetate
F0030 Ethyl Fluoroacetate
T0432 Ethyl Trifluoroacetate
F0341 Fluoromethyl Phenyl Sulfone
H0598 Ishikawa's Reagent [Fluorinating Reagent]
T1245 Methyl 4,4,4-Trifluoroacetoacetate
C1586 Methyl Chlorodifluoroacetate
F0311 Methyl Fluorosulfonyldifluoroacetate
C0991 Sodium Chlorodifluoroacetate
F0042 Trichlorofluoromethane (in cylinder without valve) [To use this product charged in cylinder, a valve is required which is sold separately (Product Code:V0030)]
F0340 Triethyl 2-Fluoro-2-phosphonoacetate
T0791 Trifluoroacetaldehyde Ethyl Hemiacetal (contains ca. 10% Ethanol)
T0433 Trifluoroacetic Anhydride
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・ヘテロ環化合物 / Heterocyclic Compounds

B3177 B3177 B3178 B3178 D3614 D3614
D3615 D3615 D3642 D3642 T1778 T1778
D3374 D3374 D2610 D2610 D1741 D1741
A1664 A1664 A1993 A1993 B2799 B2799
C2270 C2270 E0684 E0684 F0533 F0533
F0579 F0579 F0523 F0523 F0647 F0647
F0656 F0656 F0180 F0180 F0693 F0693
F0575 F0575 F0217 F0217 T2342 T2342
T2061 T2061 D2057 D2057 D3317 D3317
B3244 B3244 C1549 C1549 F0207 F0207
A1546 A1546 A2125 A2125 F0556 F0556
F0628 F0628 B2705 B2705 C2113 C2113
C1666 C1666 F0547 F0547 F0316 F0316
F0420 F0420 F0038 F0038 F0534 F0534
F0369 F0369 F0589 F0589 F0382 F0382
C2221 C2221 F0300 F0300 F0520 F0520
F0581 F0581 F0352 F0352 F0519 F0519
F0555 F0555 F0551 F0551
B3177 (2S,4R)-1-(tert-Butoxycarbonyl)-4-fluoro-2-pyrrolidinecarboxylic Acid
B3178 (2S,4S)-1-(tert-Butoxycarbonyl)-4-fluoro-2-pyrrolidinecarboxylic Acid
D3614 2'-Deoxy-2'-fluorocytidine Hydrate
D3615 2'-Deoxy-2'-fluorouridine
D3642 2'-Deoxy-5-fluorocytidine
T1778 2,3,5,6-Tetrafluoropyridine
D3374 2,4-Dichloro-5-fluoropyrimidine
D2610 2,6-Dichloro-5-fluoronicotinic Acid
D1741 2,6-Difluoropyridine
A1664 2-Amino-5-fluoropyridine
A1993 2-Amino-6-fluorobenzothiazole
B2799 2-Bromo-5-fluoropyridine
C2270 2-Chloro-5-fluoropyridine
E0684 2-Ethoxy-5-fluoro-4-pyrimidinone
F0533 2-Fluoro-3-picoline
F0579 2-Fluoro-4-picoline
F0523 2-Fluoro-5-iodopyridine
F0647 2-Fluoroadenine
F0656 2-Fluoroadenosine
F0180 2-Fluorobenzothiazole
F0693 2-Fluoroisonicotinic Acid
F0575 2-Fluoronicotinic Acid
F0217 2-Fluoropyridine
T2342 3,3,4,4-Tetrafluoropyrrolidine Hydrochloride
T2061 3,5,6-Trifluoro-2-hydroxypyridine
D2057 3,5-Dichloro-2,4,6-trifluoropyridine
D3317 3,5-Dichloro-2-fluoropyridine
B3244 3-Bromo-5-fluoropyridine
C1549 3-Chloro-2,4,5,6-tetrafluoropyridine
F0207 3-Fluoropyridine
A1546 4-Amino-2,3,5,6-tetrafluoropyridine
A2125 4-Amino-5-fluoro-2-methoxypyrimidine
F0556 4-Fluoroindole
F0628 4-Fluoropyridine Hydrochloride
B2705 5-Bromo-2-fluoropyridine
C2113 5-Chloro-2,3-difluoropyridine
C1666 5-Chloro-2,4,6-trifluoropyrimidine
F0547 5-Fluoro-2-methoxy-4-pyrimidinone
F0316 5-Fluoro-2-methylbenzothiazole
F0420 5-Fluoro-2-methylbenzoxazole
F0038 5-Fluoro-8-quinolinol
F0534 5-Fluorocytidine
F0369 5-Fluoroindole
F0589 5-Fluoroisatin
F0382 5-Fluoroorotic Acid Monohydrate
C2221 6-Chloro-2-fluoropurine
F0300 6-Fluoro-2-methylquinoline
F0520 6-Fluoro-2-picoline
F0581 6-Fluoro-3-picoline
F0352 6-Fluoroindole
F0519 7-Fluoro-2-methylquinoline
F0555 7-Fluoroindole
F0551 7-Fluoroisatin
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含フッ素生理活性化合物 / Fluorinated Bioactive Compounds

D3773 D3773 D2235 D2235 D3579 D3579
F0635 F0635 F0321 F0321 F0151 F0151
F0636 F0636 B1837 B1837 B3165 B3165
C2227 C2227 D1961 D1961 E0762 E0762
E0786 E0786 F0646 F0646 F0437 F0437
F0691 F0691 F0371 F0371 F0525 F0525
L0193 L0193 L0216 L0216 T2506 T2506
T2303 T2303 T2308 T2308 T2511 T2511
D3773 1,1-Dimethyl-3-[3-(trifluoromethyl)phenyl]urea
D2235 2'-Deoxy-5-fluorouridine
D3579 5'-Deoxy-5-fluorouridine
F0635 5-Fluoro-1-(tetrahydro-2-furfuryl)uracil
F0321 5-Fluorocytosine
F0151 5-Fluorouracil
F0636 5-Fluorouridine
B1837 Betamethasone
B3165 Betamethasone 21-Acetate
C2227 Ciprofloxacin Hydrochloride Monohydrate
D1961 Dexamethasone
E0762 Enoxacin Sesquihydrate
E0786 Enrofloxacin
F0646 Fleroxacin
F0437 Flunisolide
F0691 Fluoromethyl 1,1,1,3,3,3-Hexafluoroisopropyl Ether
F0371 Flurbiprofen
F0525 Fluticasone Propionate
L0193 Levofloxacin
L0216 Lomefloxacin Hydrochloride
T2506 Tosufloxacin p-Toluenesulfonate Hydrate
T2303 Triamcinolone
T2308 Triamcinolone Acetonide
T2511 Trifluorothymidine
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文献

1) Synthesis of fluorinated retinoic acids and their analogs
R. S. H. Liu, H. Matsumoto, A. E. Asato, M. Denny, Y. Shichida, T. Yoshizawa, F. W. Dahlquist, J. Am. Chem. Soc., 1981, 103, 7195 [DOI]; A. J. Lovey, B. A. Pawson, J. Med. Chem., 1982, 25, 71 [DOI].
2) Triethyl 2-Fluoro-2-phosphonoacetate
菊池眞仁, 小野沢孝, 有機合成化学協会誌, 1997, 55, 88.

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