Abstract
Apart from the use of (trifluoromethyl)trimethylsilane, the scope
of which has been broadened to the synthesis of trifluoromethyl
sulfides, especially those that are bio-active, new and mild processes
for the nucleophilic trifluoromethylation of non-enolizable carbonyl
compounds or disulfides have been discovered from fluoroform or
hemiaminals of trifluoroacetaldehyde and their derivatives. Very
stable hemiaminals of fluoral (as well as their silyl ethers), readily
prepared from commercially available hemiketals, have been designed
as new trifluoromethylating agents. Besides their trifluoromethylating
ability, they can be transformed into silyl or methyl ethers, which
behave, as efficient generators of α-(trifluoromethyl)iminiums
salts and equivalents of difluoromethylcarboxyl anions, respectively.
1 Introduction
2 Sulfur Trifluoromethylation with CF3SiMe3
3 Trifluoromethylation with Fluoroform
4 Trifluoromethylation with Stable Hemiaminals of Fluoral
5 Generation and Uses of Fluoral Iminiums
6 Generation and Uses of Difluorocarboxylate Anions
7 Conclusion
Key words
nucleophilic trifluoromethylation - trifluoromethyl
anion - fluoroform - fluoral hemiaminals - α,α-difluoromethyl
esters/amides
References
1a
Smart BE. In
Organofluorine
Chemistry, Principles and Commercial Applications
Banks RE.
Smart BE.
Tatlow JC.
Plenum
Press;
New York:
1994.
Chap. 3.
1b
Hiyama T.
Organofluorine Compounds, Chemistry and Applications
Springer;
Berlin:
2000.
1c
Hudlicky M.
Pavlath AE.
Chemistry
of Organic Fluorine Compounds II, A Critical Review
American
Chemical Society;
Washington DC:
1995.
ACS
Monograph 187.
2
Banks RE.
Smart BE.
Tatlow JC.
Organofluorine Chemistry,
Principles and Commercial Applications
Plenum
Press;
New York:
1994.
3
Filler R.
Kobayashi Y.
Yagupolskii LM.
Organofluorine
Compounds in Medicinal Chemistry and Biomedical Applications
Elsevier;
Amsterdam:
1993.
4
Becker A.
Inventory of Industrial Fluoro-Biochemicals
Eyrolles;
Paris:
1996.
5
Hansch C.
Leo A.
Substituent
Constants for Correlation Analysis in Chemistry and Biology
Wiley;
New
York:
1979.
6a
Umemoto T.
Kuriu Y.
Shuyama H.
Miyano O.
J. Fluorine
Chem.
1982,
20:
695
6b
Umemoto T.
Kuriu Y.
Nakayama SI.
Tetrahedron
Lett.
1982,
23:
1169
6c
Umemoto T.
Kuriu Y.
Nakayama SI.
Miyano O.
Tetrahedron Lett.
1982,
23:
1471
6d
Umemoto T.
Kuriu Y.
Nakayama SI.
Tetrahedron
Lett.
1982,
23:
4101
6e
Umemoto T.
Ishihara S.
J. Am. Chem. Soc.
1993,
115:
2156
6f
Umemoto T.
Ishihara S.
Adachi K.
J.
Fluorine Chem.
1995,
74:
77
6g
Umemoto T.
Adachi K.
J. Org. Chem.
1994,
59:
5692
7
Yang JJ.
Kirchmeier RL.
Shreeve JM.
J. Org. Chem.
1998,
63:
2656
8a
Dolbier WR. In
Organofluorine Chemistry, Fluorinated Alkenes
and Reactive Intermediates
Chambers RD.
Springer;
Berlin:
1997.
p.97-163
8b
Clavel JL.
Langlois B.
Laurent E.
Roidot N.
Phosphorus,
Sulfur Silicon
1991,
59:
169
8c
Langlois B.
Laurent E.
Roidot N.
Tetrahedron
Lett.
1991,
32:
7525
8d
Langlois B.
Laurent E.
Roidot N.
Tetrahedron
Lett.
1992,
33:
1291
8e
Langlois B.
Montègre D.
Roidot N.
J.
Fluorine Chem.
1994,
68:
63
8f
Langlois B.
Billard T.
Guérin S.
Large S.
Roidot-Perol N.
Phosphorus,
Sulfur Silicon
1999,
153-154:
323
8g
Tommasino JB.
Brondex A.
Médebielle M.
Thomalla M.
Langlois BR.
Billard T.
Synlett
2002,
1697
8h
Billard T.
Langlois B.
Large S.
Anker D.
Roidot N.
Roure P.
J. Org. Chem.
1996,
61:
7545
8i
Billard T.
Roques N.
Langlois BR.
J.
Org. Chem.
1999,
64:
3813
8j
Roques N.
Langlois BR.
Tetrahedron Lett.
2000,
41:
3069
9
McClinton MA.
McClinton DA.
Tetrahedron
1992,
48:
6555
10
Burton DJ.
Hahnfeld JL.
The Preparation
and Reactions of Fluoromethylenes In Chemistry Reviews
Vol.
8:
Tarrant P.
Marcel
Dekker Inc.;
New York:
1977.
p.153
11a
Burton DJ.
Yang ZY.
Tetrahedron
1992,
48:
189
11b
Burton DJ.
Yang ZY.
Morken PA.
Tetrahedron
1994,
50:
2993
11c
Burton DJ.
Lu L. In
Organofluorine Chemistry, Techniques and Synthons
Chambers RD.
Springer;
Berlin:
1997.
p.46-89
12a
Matsui K.
Tobita E.
Ando M.
Kondo K.
Chem.
Lett.
1981,
1719
12b
Quiclet-Sire B.
Saicic RN.
Zard SZ.
Tetrahedron
Lett.
1996,
37:
9057
12c
McNeil JG.
Burton DJ.
J.
Fluorine Chem.
1991,
55:
225
12d
Su DB.
Duan JX.
Chen QY.
Tetrahedron
Lett.
1991,
32:
7689
12e
Chen QY.
Duan JX.
Tetrahedron
Lett.
1993,
34:
4241
12f
Duan JX.
Chen QY.
J.
Chem. Soc., Perkin Trans. 1
1994,
725
12g
Roques N.
PhD
Dissertation
University Claude Bernard-Lyon I;
France:
1996.
12h Langlois B, and Roques N. inventors; WO Patent 94/01383.
13a
Prakash GKS.
Yudin AK.
Chem. Rev.
1997,
97:
757
13b
Wiedemann J.
Heiner T.
Mloston G.
Prakash GKS.
Olah GA.
Angew. Chem. Int. Ed.
1998,
37:
820
13c
Prakash GKS.
Mandal M.
J.
Fluorine Chem.
2001,
112:
123
13d
Blazejewski JC.
Anselmi E.
Wilmshurst MP.
Tetrahedron Lett.
1999,
40:
5475
13e
Prakash GKS.
Mandal M.
Olah GA.
Synlett
2001,
77
13f
Prakash GKS.
Mandal M.
Olah GA.
Org. Lett.
2001,
3:
2847
13g
Prakash GKS.
Mandal M.
Olah GA.
Angew. Chem. Int. Ed.
2001,
40:
589
13h
Prakash GKS.
Mandal M.
J.
Am. Chem. Soc.
2002,
124:
6538
14a
Singh RP.
Shreeve JM.
Tetrahedron
2000,
56:
7613
14b
Singh RP.
Cao G.
Kirchmeier RL.
Shreeve JM.
J.
Org. Chem.
1999,
64:
2873
14c
Singh RP.
Shreeve JM.
J.
Org. Chem.
2000,
65:
3241
15
Billard T.
Langlois B.
Tetrahedron Lett.
1996,
37:
6865
16
Billard T.
Large S.
Langlois B.
Tetrahedron
Lett.
1997,
38:
65
17
Bouchu MN.
Large S.
Steng M.
Langlois B.
Praly JP.
J.
Carbohydrate Res.
1998,
314:
37
18
Houston ME.
Vander Jagt DL.
Honek JF.
Bioorg. Med. Chem.
Lett.
1991,
1:
623
19
Granger CE.
Felix CP.
Parrot-Lopez H.
Langlois BR.
Tetrahedron Lett.
2000,
41:
9257
20a
Barhdadi R.
Troupel M.
Périchon J.
J. Chem. Soc., Chem.
Commun.
1998,
1251
20b
Folléas B.
Marek I.
Normant JF.
Saint-Jalmes L.
Tetrahedron
Lett.
1998,
39:
2973
20c
Folléas B.
Marek I.
Normant JF.
Saint-Jalmes L.
Tetrahedron
2000,
56:
275
20d
Russell J.
Roques N.
Tetrahedron
1998,
54:
13771
21
Shono T.
Ishifune M.
Okada T.
Kashimura S.
J. Org. Chem.
1991,
56:
2
22a
Large S.
Roques N.
Langlois BR.
J. Org. Chem.
2000,
65:
8848
22b Roques N, Russell J, Langlois B, Saint-Jalmes L, and Large S. inventors; Patent
WO 98/22435.
23
Billard T.
Bruns S.
Langlois BR.
Org.
Lett.
2000,
2:
2101
24
Billard T.
Langlois BR.
Blond G.
Tetrahedron
Lett.
2000,
41:
8777
25
Blond G.
Billard T.
Langlois BR.
Tetrahedron
Lett.
2001,
42:
2473
26
Billard T.
Langlois BR.
Blond G.
Eur.
J. Org. Chem.
2001,
1467
27
Blond G.
Billard T.
Langlois BR.
J.
Org. Chem.
2001,
66:
4826
28 Work in progress, in collaboration
with Prof G. Haufe (University of Münster, Germany).
29a
Latypov RR.
Belogai VD.
Pashkevich KI.
Izv. Akad.
Nauk, Ser. Khim.
1986,
123
29b
Takaya J.
Kagoshima H.
Akiyama T.
Org.
Lett.
2000,
2:
1577
29c
Fuchigami T.
Nakagawa Y.
Nonaka T.
J.
Org. Chem.
1987,
52:
5491
29d
Xu Y.
Dolbier WR.
Tetrahedron Lett.
1998,
39:
9151
29e
Xu Y.
Dolbier WR.
J. Org. Chem.
2000,
65:
2134
29f
Kubota T.
Ijima M.
Tanaka T.
Tetrahedron
Lett.
1992,
32:
1351
29g
Ates C.
Janousek Z.
Viehe HG.
Tetrahedron
Lett.
1993,
34:
5711
30
Billard T.
Langlois BR.
J. Org. Chem.
2002,
67:
997
31
Lebouvier N.
Laroche C.
Huguenot F.
Brigaud T.
Tetrahedron Lett.
2002,
43:
2827
32a
Xu Y.
Dolbier WR.
Rong XX.
J. Org. Chem.
1997,
62:
1576
32b
Ding Y.
Wang J.
Abboud KA.
Xu Y.
Dolbier WR.
Richards NGJ.
J. Org.
Chem.
2001,
66:
6381
33
Blond G.
Billard T.
Langlois BR.
Chem.-Eur.
J.
2002,
8:
2917
34
Van Niel MB.
Collins I.
Beer MS.
Broughton HB.
Cheng SKF.
Goodacre SC.
Heald A.
Locker KL.
MacLeod AM.
Morrison D.
Moyes CR.
O’Connor D.
Pike A.
Rowley M.
Russell MGN.
Sohal B.
Stanton JA.
Thomas S.
Verrier H.
Watt AP.
Castro JL.
J.
Med. Chem.
1999,
42:
2087
35a
Hallinan EA.
Fried J.
Tetrahedron
Lett.
1984,
25:
2301
35b
Shen Y.
Qi M.
J. Fluorine Chem.
1994,
67:
229
35c
Braun M.
Vonderhagen A.
Waldmüller D.
Liebigs Ann.
1995,
1447
35d
Lang RW.
Schaub B.
Tetrahedron Lett.
1988,
29:
2943
35e
Kitagawa O.
Taguchi T.
Kobayashi Y.
Tetrahedron
Lett.
1988,
29:
1803
35f
Tozer MJ.
Herpin TF.
Tetrahedron
1996,
8619
36a
Mcharek S.
Sibille S.
Nédélec JY.
Périchon J.
J. Organomet. Chem.
1991,
401:
211
36b
Shono T.
Kise N.
Oka H.
Tetrahedron
Lett.
1991,
32:
6567
37a
Uneyama K.
Mizutani G.
Maeda K.
Kato T.
J.
Org. Chem.
1999,
64:
6717
37b
Uneyama K.
Amii H.
J. Fluorine Chem.
2002,
114:
127
37c
Amii H.
Kobayashi T.
Uneyama K.
Synthesis
2000,
14:
2001
37d
Uneyama K.
Mizutani G.
Chem. Lett.
1999,
613
38a
Iseki K.
Kuroki Y.
Asada D.
Kobayashi Y.
Tetrahedron
Lett.
1997,
38:
1447
38b
Iseki K.
Kuroki Y.
Asada D.
Takahashi M.
Kishimo S.
Kobayashi Y.
Tetrahedron
1997,
53:
10271
39a
Ishihara T.
Yamanaka T.
Ando T.
Chem. Lett.
1984,
1165
39b
Kuroboshi M.
Ishihara T.
Tetrahedron Lett.
1987,
28:
6481
39c
Kuroboshi M.
Ishihara T.
Bull. Chem. Soc. Jpn.
1990,
63:
428
39d
Yamana M.
Ishihara T.
Ando T.
Tetrahedron
Lett.
1983,
24:
507
40
Amii H.
Kobayashi T.
Hatamoto Y.
Uneyama K.
J. Chem. Soc., Chem. Commun.
1999,
1323
41
Jin F.
Jiang B.
Xu Y.
Tetrahedron Lett.
1992,
33:
1221
42a
Brigaud T.
Doussot P.
Portella C.
J. Chem. Soc., Chem. Commun.
1994,
2117
42b
Lefebvre O.
Brigaud T.
Portella C.
Tetrahedron
1998,
54:
5939
42c
Lefebvre O.
Brigaud T.
Portella C.
J.
Org. Chem.
2001,
66:
1941
42d
Saleur D.
Brigaud T.
Bouillon JP.
Portella C.
Synlett
1999,
4:
432
42e
Saleur D.
Bouillon JP.
Portella C.
J.
Org. Chem.
2001,
66:
4543
42f
Saleur D.
Brigaud T.
Bouillon JP.
Portella C.
Tetrahedron
1999,
55:
7233
42g
Lefebvre O.
Brigaud T.
Portella C.
J.
Org. Chem.
2001,
66:
4348
42h
Brigaud T.
Lefebvre O.
Plantier-Royon R.
Portella C.
Tetrahedron Lett.
1996,
37:
6115
42i
Berber H.
Brigaud T.
Lefebvre O.
Plantier-Royon R.
Portella C.
Chem.-Eur.
J.
2001,
7:
903
43
Kodama Y.
Yamane H.
Okumura M.
Shiro M.
Tetrahedron
1995,
51:
12217
44a
Broadhurst MJ.
Percy JM.
Prime ME.
Tetrahedron Lett.
1997,
38:
5903
44b
Broadhurst MJ.
Brown SJ.
Percy JM.
Prime ME.
J.
Chem. Soc., Perkin Trans. 1
2000,
3217
44c
Kariuki BM.
Owton WM.
Percy JM.
Pintat S.
Smith CA.
Spencer SC.
Thomas AC.
Watson M.
J.
Chem. Soc., Chem. Commun.
2002,
228
44d
Howarth JA.
Owton WM.
Percy JM.
Rock MH.
Tetrahedron
1995,
37:
10289
44e
Howarth JA.
Owton WM.
Percy JM.
J. Chem. Soc., Chem. Commun.
1995,
757
45a
Médebielle M.
Keyrouz R.
Langlois B.
Billard T.
Dolbier WR.
Burkholder C.
Ait-Mohand S.
Okada E.
Ashida T.
Electron
Transfer Methodologies to the Synthesis of Organo-Fluorine Compounds
In Recent Research Development in Electron
Transfer Reactions in Organic Synthesis
Vanelle P.
Research Signpost;
Trivandrum:
2002.
p.89-97
45b
Billard T.
Langlois BR.
Médebielle M.
Tetrahedron Lett.
2001,
42:
3463