G. Weinheim, S. J. Keding, and S. J. Danishefsky, Synthetic Carbohydrate Vaccines In Carbohydrate-Based Drug Discovery, p.381, 2003.

J. Beijnen, H. Zwierzina, H. M. Pinedo, A. Simmons, G. Mayrhofer et al., Cancer Res 5 (a) Grubor-Bauk, J. Immunol, vol.8, issue.170, pp.3702-3709, 2002.

G. Weinheim, (b) Carbohydrate-Based Drud Discovery, 2002.

S. J. Keding and S. J. Danishefsky, Synthetic Carbohydrate Vaccines, Carbohydrate-Based Drug

M. Kronenberg, TOWARD AN UNDERSTANDING OF NKT CELL BIOLOGY: Progress and Paradoxes, Annual Review of Immunology, vol.23, issue.1, pp.877-900, 2005.
DOI : 10.1146/annurev.immunol.23.021704.115742

C. Mathé and G. Gosselin, Antiviral Res, Cancer Sci, vol.71, issue.95, pp.276-281, 2004.

H. Mitsuya, R. Yarchoan, and S. Broder, Molecular targets for AIDS therapy, Science, vol.249, issue.4976, pp.1533-1544, 1990.
DOI : 10.1126/science.1699273

P. Sears and C. Wong, Carbohydrate Mimetics: A New Strategy for Tackling the Problem of Carbohydrate-Mediated Biological Recognition, Angewandte Chemie International Edition, vol.38, issue.16, pp.2300-2324, 1999.
DOI : 10.1002/(SICI)1521-3773(19990816)38:16<2300::AID-ANIE2300>3.0.CO;2-6

T. Natori, Y. Koezuka, and T. Higa, Agelasphins, novel ??-galactosylceramides from the marine sponge Agelas mauritianus, Tetrahedron Letters, vol.34, issue.35, pp.5591-5592, 1993.
DOI : 10.1016/S0040-4039(00)73889-5

K. Akimoto, T. Natori, and M. Morita, Synthesis and stereochemistry of agelasphin-9b, Tetrahedron Letters, vol.34, issue.35, pp.5593-5595, 1993.
DOI : 10.1016/S0040-4039(00)73890-1

D. I. Godfrey, M. Kronenberg, and N. A. Borg, Going both ways: Immune regulation via CD1d-dependent NKT cells, Journal of Clinical Investigation, vol.114, issue.10, pp.1379-1388, 2004.
DOI : 10.1172/JCI200423594
URL : http://www.ncbi.nlm.nih.gov/pmc/articles/PMC525753

L. Linsen, V. Somers, and P. Stinissen, Immunoregulation of Autoimmunity by Natural Killer T Cells, Human Immunology, vol.66, issue.12, pp.1193-1202, 2005.
DOI : 10.1016/j.humimm.2006.02.020

K. Murata, T. Toba, K. Nakanishi, B. Takahashi, T. Yamamura et al., -Galactosyl)-2- tetracosanoylamino-1,3,4-nonanetriol, The Journal of Organic Chemistry, vol.70, issue.6, pp.2398-2401, 2005.
DOI : 10.1021/jo048151y
URL : https://hal.archives-ouvertes.fr/in2p3-01333933

E. Kobayashi, K. Motoki, Y. Yamagushi, T. Uchida, H. Fukushima et al., Enhancing effects of ??-, ??-monoglycosylceramides on natural killer cell activity, Bioorganic & Medicinal Chemistry, vol.4, issue.4, pp.615-619, 1996.
DOI : 10.1016/0968-0896(96)00049-1

G. Xing, D. Wu, M. A. Poles, A. Horowitz, M. Tsuli et al., Synthesis and human NKT cell stimulating properties of 3-O-sulfo-??/??-galactosylceramides, Bioorganic & Medicinal Chemistry, vol.13, issue.8, pp.2907-2916, 2005.
DOI : 10.1016/j.bmc.2005.02.018

X. H. Zhu, A. Hara, and T. Taketomi, The Existence of Galactosylceramide I3-Sulfate in Serums of Various Mammals and Its Anticoagulant Activity1, The Journal of Biochemistry, vol.110, issue.2, pp.241-245, 1991.
DOI : 10.1093/oxfordjournals.jbchem.a123564

X. Zhou, C. Forestier, R. D. Goff, C. Li, L. Teyton et al., Synthesis and NKT Cell Stimulating Properties of Fluorophore- and Biotin-Appended 6?????????-Amino-6?????????-deoxy-galactosylceramides, Organic Letters, vol.4, issue.8, pp.1267-1270, 2002.
DOI : 10.1021/ol025565+

T. Tashiro, R. Nakagawa, S. Inoue, M. Shiozaki, H. Watarai et al., RCAI-61, the 6???-O-methylated analog of KRN7000: its synthesis and potent bioactivity for mouse lymphocytes to produce interferon-?? in vivo, Tetrahedron Letters, vol.49, issue.48, pp.6827-6830, 2008.
DOI : 10.1016/j.tetlet.2008.09.074

T. Tashiro, R. Nakagawa, T. Hirokawa, S. Inoue, H. Watarai et al., RCAI-56, a carbocyclic analogue of KRN7000: its synthesis and potent activity for natural killer (NK) T cells to preferentially produce interferon-??, Tetrahedron Letters, vol.48, issue.19, pp.3343-3347, 2007.
DOI : 10.1016/j.tetlet.2007.03.074

M. Fujio, D. Wu, R. Garcia-navarro, . D. Ho, M. Tsuji et al., Structure-Based Discovery of Glycolipids for CD1d-Mediated NKT Cell Activation:?? Tuning the Adjuvant versus Immunosuppression Activity, Journal of the American Chemical Society, vol.128, issue.28, pp.9022-9023, 2006.
DOI : 10.1021/ja062740z

T. Lee, Synthesis and Evaluation of 1,2,3-Triazole Containing Analogues of the Immunostimulant ??-GalCer, Journal of Medicinal Chemistry, vol.50, issue.3, pp.585-589, 2007.
DOI : 10.1021/jm061243q

G. Yang, J. Schmieg, M. Tsuji, and R. W. Franck, The C-Glycoside Analogue of the Immunostimulant??-Galactosylceramide (KRN7000): Synthesis and Striking Enhancement of Activity, Angewandte Chemie International Edition, vol.43, issue.29, pp.3818-3822, 2004.
DOI : 10.1002/anie.200454215

R. W. Franck and M. Tsuji, -Galactosylceramides:?? Synthesis and Immunology, Accounts of Chemical Research, vol.39, issue.10, pp.692-701, 2006.
DOI : 10.1021/ar050006z
URL : https://hal.archives-ouvertes.fr/hal-00607361

J. Schmieg, G. Yang, R. W. Franck, and M. Tsuji, Superior Protection against Malaria and Melanoma Metastases by a C-glycoside Analogue of the Natural Killer T Cell Ligand ??-Galactosylceramide, The Journal of Experimental Medicine, vol.8, issue.11, pp.1631-1641, 2003.
DOI : 10.1046/j.1423-0410.2002.00217.x

T. Toba, K. Murata, T. Yamamura, S. Miyake, and H. Annoura, A concise synthesis of (3S,4S,5R)-1-(??-d-galactopyranosyl)-3-tetracosanoylamino-4,5-decanediol, a C-glycoside analogue of immunomodulating ??-galactosylceramide OCH, Tetrahedron Letters, vol.46, issue.30, pp.5043-5047, 2005.
DOI : 10.1016/j.tetlet.2005.05.069

R. T. Dere and X. Zhu, The First Synthesis of a Thioglycoside Analogue of the Immunostimulant KRN7000, Organic Letters, vol.10, issue.20, pp.4641-4644, 2008.
DOI : 10.1021/ol8019555

M. Shimizu and T. Hiyama, Modern Synthetic Methods for Fluorine-Substituted Target Molecules, Angewandte Chemie International Edition, vol.10, issue.2, pp.214-231, 2005.
DOI : 10.1002/anie.200460441

I. Ojima, J. T. Mccarthy, and D. Hagan, Biomedical Frontiers of Fluorine Chemistry, ACS Symposium Series Chem. Soc. Rev. J.-P.; Bonnet-Delpon, D. in Bioorganic and Medicinal Chemistry of Fluorine, vol.639, issue.37, pp.65-308, 1996.
DOI : 10.1021/bk-1996-0639

M. S. Smyth and T. R. Burke, Enantioselective synthesis of N-boc and N-fmoc protected diethyl 4-phosphono(difluoromethyl)-L-phenylalanine; agents suitable for the solid-phase synthesis of peptides containing nonhydrolyzable analogues of O-phosphotyrosine, Tetrahedron Letters, vol.35, issue.4, pp.551-554, 1994.
DOI : 10.1016/S0040-4039(00)75835-7

S. G. 70-withers, I. P. Street, P. Bird, D. H. Dolphin, S. G. Withers et al., 2-Deoxy-2-fluoroglucosides: a novel class of mechanism-based glucosidase inhibitors, Journal of the American Chemical Society, vol.109, issue.24, pp.7530-7531, 1987.
DOI : 10.1021/ja00258a047

A. Alavi and M. Reivich, Guest editorial: The conception of FDG-PET imaging, Seminars in Nuclear Medicine, vol.32, issue.1, pp.2-5, 1956.
DOI : 10.1053/snuc.2002.29269

O. Warburg, The metabolism of tumors. L o n d o n : Arnold Constable, 1930.

R. Filler and S. Riputana, Fluorine in medicinal chemistry: a century of progress and a 60-year retrospective of selected highlights, Future Medicinal Chemistry, vol.1, issue.5, pp.777-791, 2009.
DOI : 10.4155/fmc.09.65

A. Deleuze, C. Menozzi, M. Sollogoub, and P. Sinaÿ, -glucose: A Step Further in Sugar Mimesis, Angewandte Chemie International Edition, vol.37, issue.48, pp.6680-6683, 2004.
DOI : 10.1002/anie.200461244
URL : https://hal.archives-ouvertes.fr/pastel-00537861

F. Barth, C. O-yang, and A. Arnone, Cyclization of ??,??-Difluoromethyl Radicals: A New Route to the Preparation of Difluorocyclopentane Derivatives, Tetrahedron Letters, vol.32, issue.42, pp.5873-5876, 1991.
DOI : 10.1016/S0040-4039(00)79414-7

S. Jiang, G. Singh, and A. S. Batsanov, Synthesis of a difluorinated carbasugar from d-ribose via intramolecular nitrone cycloaddition reaction, Tetrahedron: Asymmetry, vol.11, issue.19, pp.3873-3877, 2000.
DOI : 10.1016/S0957-4166(00)00367-0

G. Fourrière, J. Lalot, N. Van-hijfte, J. C. Quirion, and E. Leclerc, Synthesis of difluorinated carbocyclic analogues of 5-deoxypentofuranoses, Tetrahedron Letters, vol.50, issue.50, pp.7048-7050, 2009.
DOI : 10.1016/j.tetlet.2009.09.170

J. Jimenez-barbero, R. Demange, K. Schenk, and P. Vogel, -Disaccharide, The Journal of Organic Chemistry, vol.66, issue.15, pp.5132-5138, 2001.
DOI : 10.1021/jo0102462
URL : https://hal.archives-ouvertes.fr/hal-00310095

T. F. Herpin, W. B. Motherwell, and M. T. Tozer, The synthesis of difluoromethylene-linked C-glycosides and C-disaccharides, Tetrahedron: Asymmetry, vol.5, issue.11, pp.2269-2282, 1994.
DOI : 10.1016/S0957-4166(00)86305-3

H. Berber, T. Brigaud, O. Lefebvre, R. Plantier-royon, and C. Portella, Reactions of Difluoroenoxysilanes with Glycosyl Donors: Synthesis of Difluoro-C-glycosides and Difluoro-C-disaccharides, Chemistry, vol.32, issue.4, pp.903-909, 2001.
DOI : 10.1002/1521-3765(20010216)7:4<903::AID-CHEM903>3.0.CO;2-M

G. Hirai, T. Watanabe, K. Yamaguchi, T. Miyagi, and M. Sodeoka, -Linked Ganglioside GM4, Journal of the American Chemical Society, vol.129, issue.50, pp.15420-15421, 2007.
DOI : 10.1021/ja075738w
URL : https://hal.archives-ouvertes.fr/in2p3-00012162

S. Marcotte, F. D-'hooge, S. Ramadas, C. Feasson, X. Pannecoucke et al., Synthesis of new ??- and ??-gem-difluoromethylene C-glycosides in the galactose and glucose series, Tetrahedron Letters, vol.42, issue.34, pp.5879-5882, 2001.
DOI : 10.1016/S0040-4039(01)01144-3

F. Poulain, A. Serre, J. Lalot, E. Leclerc, and J. Quirion, -mannosides and Their Conversion to Fluorinated Pseudoglycopeptides, The Journal of Organic Chemistry, vol.73, issue.6, pp.2435-2438, 2008.
DOI : 10.1021/jo702466h
URL : https://hal.archives-ouvertes.fr/hal-00857495

F. Poulain, E. Leclerc, and J. Quirion, Approaches to the synthesis of CF2-analogues of 2-deoxy-2-aminoglycosides, Tetrahedron Letters, vol.50, issue.16, pp.1803-805, 2009.
DOI : 10.1016/j.tetlet.2009.01.155

B. Moreno, C. Quehen, M. Rose-hélène, E. Leclerc, and J. Quirion, -Glycosides, Organic Letters, vol.9, issue.13, pp.2477-2480, 2007.
DOI : 10.1021/ol070835f
URL : https://hal.archives-ouvertes.fr/hal-00807126

J. Dolbier, W. R. Hu, J. Zhang, and W. , Structure, Reactivity, and Chemistry of Fluoroalkyl Radicals, Chemical Reviews, vol.96, issue.5, pp.1557-1584, 1996.
DOI : 10.1021/cr941142c

D. Morel, F. Dawans, A. Ando, and I. Kumadaki, Synthese d'un nouveau monomere hydrofluorocarboxylique le difluoro-2,2-butene-3-oate d'ethyle, Pour d'autres additions radicalaires de BrCF 2 CO 2 Et, pp.1445-1447, 1977.
DOI : 10.1016/0040-4020(77)88002-2

J. Bégué, Bonnet-Delpon, D. in Bioorganic and Medicinal Chemistry of Fluorine, pp.1-22, 2008.

L. A. Buttle and W. B. Motherwell, Comparative studies on the generation and cyclisation reactions of difluoroalkyl radicals, Tetrahedron Letters, vol.35, issue.23, pp.3995-3998, 1994.
DOI : 10.1016/S0040-4039(00)76723-2

N. A. Lebel, R. F. Czaja, A. Deboer, and A. L. Beckwith, Stereochemistry of free-radical additions of thiols to substituted cyclohexenes, The Journal of Organic Chemistry, vol.34, issue.10, pp.3112-3126, 1969.
DOI : 10.1021/jo01262a070

F. W. Lichtenthaler, M. Lergenmüller, S. Peters, and Z. Varga, manno- versus gluco-Selectivity in reductions of 2-keto-??-d-arabino-hexopyranosides, Tetrahedron: Asymmetry, vol.14, issue.6, pp.727-736, 2003.
DOI : 10.1016/S0957-4166(03)00028-4

L. Cipolla, B. La-ferla, L. Lay, F. Peri, and F. Nicotra, Stereoselective synthesis of ??-C-glycosides of N-acetylgalactosamine, Tetrahedron: Asymmetry, vol.11, issue.1, pp.295-303, 2000.
DOI : 10.1016/S0957-4166(99)00480-2

A. K. Dilger, V. Gopalsamuthiram, and S. D. Burke, A Two-Directional Approach to a (???)-Dictyostatin C11???C23 Segment:?? Development of a Highly Diastereoselective, Kinetically-Controlled Meerwein???Ponndorf???Verley Reduction, Journal of the American Chemical Society, vol.129, issue.51, pp.16273-16277, 2007.
DOI : 10.1021/ja077336u

E. Jahnke and R. R. Tykwinski, The Fritsch???Buttenberg???Wiechell rearrangement: modern applications for an old reaction, Chemical Communications, vol.14, issue.19, pp.3235-3249, 2010.
DOI : 10.1351/PAC-CON-09-09-04

P. Kumar, A. Dubbey, and V. G. Puranik, A general and concise asymmetric synthesis of sphingosine, safingol and phytosphingosines via tethered aminohydroxylation, Organic & Biomolecular Chemistry, vol.35, issue.22, pp.5074-5086, 2010.
DOI : 10.1039/c0ob00117a

H. Yoda, T. Oguchi, and K. Takabe, An expeditious and practical synthetic process for phytosphingosine and tetrahydroxy-LCB from D-glutamic acid, Tetrahedron: Asymmetry, vol.7, issue.7, pp.2113-2116, 1996.
DOI : 10.1016/0957-4166(96)00254-6

O. Shirota, K. Nakanishi, and N. Berova, Phytosphingosines ??? a facile synthesis and spectroscopic protocol for configurational assignment, Tetrahedron, vol.55, issue.48, pp.13643-13658, 1999.
DOI : 10.1016/S0040-4020(99)00839-X

L. He, H. S. Byun, and R. Bittman, A Stereocontrolled, Efficient Synthetic Route to Bioactive Sphingolipids:?? Synthesis of Phytosphingosine and Phytoceramides from Unsaturated Ester Precursors via Cyclic Sulfate Intermediates, The Journal of Organic Chemistry, vol.65, issue.22, pp.7618-7626, 2000.
DOI : 10.1021/jo001225v

J. R. Dulayymi, M. S. Baird, and E. Roberts, The synthesis of a single enantiomer of a major ??-mycolic acid of M. tuberculosis, Tetrahedron, vol.61, issue.50, pp.11939-11951, 2005.
DOI : 10.1016/j.tet.2005.09.056

H. Azuma, S. Tamagaki, and K. Ogino, -Serine, The Journal of Organic Chemistry, vol.65, issue.11, pp.3538-3541, 2000.
DOI : 10.1021/jo991447x
URL : https://hal.archives-ouvertes.fr/hal-00309399

J. Joo, V. Pham, Y. Tian, Y. Cung, and C. Oh, Stereoselective synthesis of (+)-polyoxamic acid based on the synthesis of chiral oxazine, Organic & Biomolecular Chemistry, vol.67, issue.8, pp.1498-1501, 2008.
DOI : 10.1039/b717961h

L. Tamborini, P. Conti, S. Colleoni, M. Gobbi, and C. De-micheli, Synthesis of new ??- and ??-benzyloxy-S-glutamic acid derivatives and evaluation of their activity as inhibitors of excitatory amino acid transporters, Tetrahedron, vol.65, issue.31, pp.6083-6089, 2009.
DOI : 10.1016/j.tet.2009.05.054

J. E. Booker, A. Boto, G. H. Churchill, C. P. Green, M. Ling et al., Approaches to the quaternary stereocentre and to the heterocyclic core in diazonamide A using the Heck reaction and related coupling reactions, Organic & Biomolecular Chemistry, vol.46, issue.22, pp.4193-4205, 2006.
DOI : 10.1039/b609604b

F. Calabi, J. M. Jarvis, L. Martin, and C. Milstein, Two classes of CD1 genes, European Journal of Immunology, vol.12, issue.2, pp.285-292, 1989.
DOI : 10.1002/eji.1830190211

D. Wu, M. Fujio, and C. H. Wong, Glycolipids as immunostimulating agents, Bioorganic & Medicinal Chemistry, vol.16, issue.3, pp.1073-1083, 2008.
DOI : 10.1016/j.bmc.2007.10.026
URL : http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2279229

N. 129-burdin, L. Brossay, and M. Kronenberg, Immunization with ??-galactosylceramide polarizes CD1-reactive NK T cells towards Th2 cytokine synthesis, European Journal of Immunology, vol.5, issue.6, pp.2014-2025, 1999.
DOI : 10.1002/(SICI)1521-4141(199906)29:06<2014::AID-IMMU2014>3.0.CO;2-G

V. Parietti, H. Chifflot, J. Sibilia, S. Muller, and F. Monneaux, Rituximab treatment overcomes reduction of regulatory iNKT cells in patients with rheumatoid arthritis, Clinical Immunology, vol.134, issue.3, pp.331-339, 2010.
DOI : 10.1016/j.clim.2009.11.007
URL : https://hal.archives-ouvertes.fr/hal-00450669

S. Liu, J. Xie, W. Li, W. Kong, L. Wang et al., Highly Enantioselective Synthesis of Chiral Cyclic Amino Alcohols and Conhydrine by Ruthenium-Catalyzed Asymmetric Hydrogenation, Organic Letters, vol.11, issue.21, pp.4994-4997, 2009.
DOI : 10.1021/ol901605a

B. Aguilera, A. Fernández-mayoralas, and C. Jaramillo, Use of cyclic sulfamidates derived from D-allosamine in nucleophilic displacements: Scope and limitations, Tetrahedron, vol.53, issue.16, pp.5863-5876, 1997.
DOI : 10.1016/S0040-4020(97)00246-9

S. L. Cobb and J. C. Vederas, A concise stereoselective synthesis of orthogonally protected lanthionine and ??-methyllanthionine, Org. Biomol. Chem., vol.50, issue.7, pp.1031-1038, 2007.
DOI : 10.1039/B618178C

. Anal, Found: C, 72.21; H, 8.13; N, (d, J = 8.7 Hz, 1H, H 1 ), 4.97 (s, 1H, 12H, CH 2 Ph and H 2-8 )9 ), 4.01 (s, 1H, H 3 ), 3.93 (s, 1H, pp.4-68

. Anal, Calcd for C 59 H 75 F 2 NO 9 : C, 72.29; H, 7.71; N, 1.43. Found: C, 72.36; H, 7.73, pp.1-44

. Anal, Found: C, 76.03; H, 9.48, 1H, H 2 or H 8 ), 4.47-4.46 (m, 1H, H 2 or H 8, pp.11-12

F. Nmr, 5 MHz, CDCl 3 ): ' -113.2 (s, 2F)

D. Competences, L. Et, . J. @bullet-membre-de-l, and . Danishefsky, Synthesis of fluorinated -Galactosylceramide by Addition of Electrophilic Radical to Glycals DOMAINESADIRCOF : association des doctorants de l'IRCOF [1] a) S, J. R. Allen, Angew. Chem, vol.112, p.882, 2000.

S. J. Keding, 39, 836; b) S Danishefsky in Carbohydrate-Based Drug Discovery, Angew. Chem. Int. Ed, vol.1, 2000.

T. Natori, M. Morita, K. Akimoto, and Y. Koezuka, Agelasphins, novel antitumor and immunostimulatory cerebrosides from the marine sponge Agelas mauritianus, Tetrahedron, vol.50, issue.9, pp.2771-2784, 1994.
DOI : 10.1016/S0040-4020(01)86991-X

). P. Kirsch-in-modern-fluoroorganic-chemistry, . Wiley-vch, . J. Weinheim-b-)-h, D. Bçhm, S. Banner et al., Bonnet-Delpon in Bioorganic and Medicinal Chemistry of Fluorine, Chem. Soc. Rev, vol.5, issue.37, pp.237-277, 2004.

S. Houlton, W. B. Motherwell, B. C. Ross, M. J. Tozer, D. J. Williams et al., A convenient strategy for replacement of the anomeric hydroxyl group by difluoromethyl functionality in carbohydrate derivatives, Herpin, W. B. Motherwell, J.-M, pp.8087-8106, 1993.
DOI : 10.1016/S0040-4020(01)88029-7

R. S. Timofte, B. Linclau, . Org, and . Lett, For a related cyclization of a difluoromethyllithium species, see: a), pp.3673-3676, 2008.

A. J. Linclau, R. S. Boydell, K. J. Timofte, V. Brown, A. C. Vinader et al., Enantioselective synthesis of tetrafluorinated ribose and fructose, Organic & Biomolecular Chemistry, vol.36, issue.4, pp.803-814, 2009.
DOI : 10.1039/b817260a

W. Gmbh and &. Co, KGaA, Weinheim www.chemeurj.org 5241 COMMUNICATION Straightforward Preparation of Functionalized a-CF 2 -Galactosides