目前許多研究指出醣蛋白上的醣體與癌症轉移、免疫反應、蛋白質摺疊和穩定性皆有相關。後轉譯修飾使蛋白質上含有各式各樣的寡醣體，不同的寡醣體對於蛋白質有不同的影響。為研究寡醣體對於醣蛋白活性的影響，因此發展有效率的方式合成N-glycan五醣核心是相當重要且仍具挑戰的目標。
本論文之目的在於合成對生物有重要影響的N-glycan還原端之三醣體。合成策略上，先合成最困難的甘露醣-乙醯葡萄醣胺雙醣體，將二號位置為芐基、三號位置為4-甲氧基芐基和四、六號位置為苯亞甲基作為保護基的甘露醣予體和一號位置為叔丁基二甲基矽、二號位置為磷苯二甲酸酯保護之胺基、和三、六號位置為芐基保護的受體，利用三氟甲磺酸酐 (Tf2O)、苯亞磺醯哌啶 (BSP) 和2,4,6-三叔丁基嘧啶 (TTBP) 等試劑促進行醣基化反應，合成1,2-順式甘露醣之醣苷鍵，且有良好的位向選擇性及產率。將雙醣轉換成予體後，與帶有氟標記的葡萄糖胺受體進行連結，由於雙醣予體的二號位置為帶有鄰基參與效應的保護基團，因此得到單一位向的三醣體。

1. Bertozzi, C. R.; Kiessling, L. L., Chemical Glycobiology. Science 2001, 291 (5512), 2357-2364.
2. (a) Ritchie, G. E.; Moffatt, B. E.; Sim, R. B.; Morgan, B. P.; Dwek, R. A.; Rudd, P. M., Glycosylation and the Complement System. Chem. Rev. 2002, 102 (2), 305-320; (b) Lis, H.; Sharon, N., Lectins:  Carbohydrate-Specific Proteins That Mediate Cellular Recognition. Chem. Rev. 1998, 98 (2), 637-674.
3. (a) Wong, C.-H., Protein Glycosylation:  New Challenges and Opportunities. J. Org. Chem. 2005, 70 (11), 4219-4225; (b) Parker, R. B.; Kohler, J. J., Regulation of Intracellular Signaling by Extracellular Glycan Remodeling. ACS Chem. Biol. 2009, 5 (1), 35-46.
4. Varki, A.; Cummings, R.; Esko, J.; Freeze, H.; Hart, G. and Marth, J., Essentials of Glycobiology (NY, Cold Spring Harbor) 1999.
5. Kobata, A., Glycobiology: an expanding research area in carbohydrate chemistry. Acc. Chem. Res. 1993, 26 (6), 319-324.
6. Helenius, A.; Aebi; Markus, Intracellular Functions of N-Linked Glycans. Science 2001, 291 (5512), 2364-2369.
7. (a) Crocker, P. R.; Feizi, T., Carbohydrate recognition systems: functional triads in cell-cell interactions. Curr. Opin. Struct. Biol. 1996, 6 (5), 679-691; (b) Lee, Y. C.; Lee, R. T., Carbohydrate-Protein Interactions: Basis of Glycobiology. Acc. Chem. Res. 1995, 28 (8), 321-327; (c) Lis, H.; Sharon, N., Lectins: Carbohydrate-Specific Proteins That Mediate Cellular Recognition. Chem. Rev. 1998, 98 (2), 637-674.
8. Feizi, T., Demonstration by monoclonal antibodies that carbohydrate structures of glycoproteins and glycolipids are onco-developmental antigens. Nature 1985, 314 (6006), 53-57.
9. (a) Mackiewicz, A.; Khan, M. A.; Gorny, A.; Kapcinska, M.; Juszczyk, J.; Calabrese, L. H.; Espinosa, L. R., Glycoforms of alpha 1-acid glycoprotein in sera of human immunodeficiency virus-infected persons. J. Infect. Dis. 1994, 169 (6), 1360-3; (b) van Dijk, W.; van der Stelt, M. E.; Salera, A.; Dente, L., Effect of transgenic expression of human alpha 1-acid glycoprotein (AGP) on the glycosylation of human and mouse AGP in various transgenic mouse sera. Eur. J. Cell. Biol. 1991, 55 (1), 143-148.
10. Andre, S.; Kozar, T.; Schuberth, R.; Unverzagt, C.; Kojima, S.; Gabius, H. J., Substitutions in the N-glycan core as regulators of biorecognition: the case of core-fucose and bisecting GlcNAc moieties. Biochemistry 2007, 46 (23), 6984-6995.
11. Watt, G. M.; Boons, G. J., A convergent strategy for the preparation of N-glycan core di-, tri-, and pentasaccharide thioaldoses for the site-specific glycosylation of peptides and proteins bearing free cysteines. Carbohydr. Res. 2004, 339 (2), 181-193.
12. Baek, J. Y.; Lee, B.-Y.; Jo, M. G.; Kim, K. S., β-Directing Effect of Electron-Withdrawing Groups at O-3, O-4, and O-6 Positions and α-Directing Effect by Remote Participation of 3-O-Acyl and 6-O-Acetyl Groups of Donors in Mannopyranosylations. J. Am. Chem. Soc. 2009, 131 (48), 17705-17713.
13. Dan, A.; Ito, Y.; Ogawa, T., Stereocontrolled synthesis of the pentasaccharide core structure of asparagine-linked glycoprotein oligosaccharide based on a highly convergent strategy. Tetrahedron Lett. 1995, 36 (41), 7487-7490.
14. Chayajarus, K.; Chambers, D. J.; Chughtai, M. J.; Fairbanks, A. J., Stereospecific synthesis of 1,2-cis glycosides by vinyl-mediated IAD. Org. Lett. 2004, 6 (21), 3797-800.
15. Wu, X.; Schmidt, R. R., Solid-phase synthesis of complex oligosaccharides using a novel capping reagent. J. Org. Chem. 2004, 69 (6), 1853-1857.
16. Weingart, R.; Schmidt, R. R., Can preferential β-mannopyranoside formation with 4,6-O-benzylidene protected mannopyranosyl sulfoxides be reached with trichloroacetimidates? Tetrahedron Lett. 2000, 41 (45), 8753-8758.
17. Sun, B.; Srinivasan, B.; Huang, X., Pre-Activation-Based One-Pot Synthesis of an α-(2,3)-Sialylated Core-Fucosylated Complex Type Bi-Antennary N-Glycan Dodecasaccharide. Chem. -Eur. J. 2008, 14 (23), 7072-7081.
18. Crich, D.; Dudkin, V., Why are the hydroxy groups of partially protected N-acetylglucosamine derivatives such poor glycosyl acceptors, and what can be done about it? A comparative study of the reactivity of N-acetyl-, N-phthalimido-, and 2-azido-2-deoxy-glucosamine derivatives in glycosylation. 2-Picolinyl ethers as reactivity-enhancing replacements for benzyl ethers. J. Am. Chem. Soc. 2001, 123 (28), 6819-6825.
19. Wang, P.; Zhu, J.; Yuan, Y.; Danishefsky, S. J., Total synthesis of the 2,6-sialylated immunoglobulin G glycopeptide fragment in homogeneous form. J. Am. Chem. Soc. 2009, 131 (46), 16669-16671.
20. Crich, D.; Xu, H., Direct stereocontrolled synthesis of 3-amino-3-deoxy-beta-mannopyranosides: importance of the nitrogen protecting group on stereoselectivity. J. Org. Chem. 2007, 72 (14), 5183-5192.
21. (a) Fraser-Reid, B.; Wu, Z.; Andrews, C. W.; Skowronski, E.; Bowen, J. P., Torsional effects in glycoside reactivity: saccharide couplings mediated by acetal protecting groups. J. Am. Chem. Soc. 1991, 113 (4), 1434-1435; (b) Andrews, C. W.; Rodebaugh, R.; Fraser-Reid, B., A Solvation-Assisted Model for Estimating Anomeric Reactivity. Predicted versus Observed Trends in Hydrolysis of n-Pentenyl Glycosides1. J. Org. Chem. 1996, 61 (16), 5280-5289; (c) Jensen, H. H.; Nordstrøm, L. U.; Bols, M., The Disarming Effect of the 4,6-Acetal Group on Glycoside Reactivity:  Torsional or Electronic? J. Am. Chem. Soc. 2004, 126 (30), 9205-9213.
22. Crich, D.; Jayalath, P.; Hutton, T. K., Enhanced diastereoselectivity in beta-mannopyranosylation through the use of sterically minimal propargyl ether protecting groups. J. Org. Chem. 2006, 71 (8), 3064-3070.
23. Crich, D.; Li, L.; Shirai, M., The 4-(tert-butyldiphenylsiloxy)-3-fluorobenzyl group: a new alcohol protecting group, fully orthogonal with the p-methoxybenzyl group and removable under desilylation conditions. J. Org. Chem. 2009, 74 (6), 2486-2493.
24. Boltje, T. J.; Li, C.; Boons, G. J., Versatile set of orthogonal protecting groups for the preparation of highly branched oligosaccharides. Org. Lett. 2010, 12 (20), 4636-4639.
25. Chang, S. S.; Shih, C. H.; Lai, K. C.; Mong, K. K., Rate-dependent inverse-addition beta-selective mannosylation and contiguous sequential glycosylation involving beta-mannosidic bond formation. Chem. Asian J. 2010, 5 (5), 1152-1162.
26. Gladysz, J. A., Curran, D. P., Horvath, I. T., Eds., Handbook of fluorous chemistry. 2004.
27. Horvath, I. T.; Rabai, J., Facile catalyst separation without water: fluorous biphase hydroformylation of olefins. Science 1994, 266 (5182), 72-75.
28. (a) Curran, D. P.; Hadida, S.; He, M., Thermal Allylations of Aldehydes with a Fluorous Allylstannane. Separation of Organic and Fluorous Products by Solid Phase Extraction with Fluorous Reverse Phase Silica Gel. J. Org. Chem. 1997, 62 (20), 6714-6715; (b) Luo, Z.; Williams, J.; Read, R. W.; Curran, D. P., Fluorous Boc (FBoc) Carbamates:  New Amine Protecting Groups for Use in Fluorous Synthesis. J. Org. Chem. 2001, 66 (12), 4261-4266; (c) Zhang, W.; Lu, Y.; Chen, C. H.-T.; Curran, D. P.; Geib, S., Fluorous Synthesis of Hydantoin-, Piperazinedione-, and Benzodiazepinedione-Fused Tricyclic and Tetracyclic Ring Systems. Eur. J. Org. Chem. 2006, 2006 (9), 2055-2059; (d) Dakas, P. Y.; Barluenga, S.; Totzke, F.; Zirrgiebel, U.; Winssinger, N., Modular synthesis of radicicol A and related resorcylic acid lactones, potent kinase inhibitors. Angew. Chem., Int. Ed. Engl. 2007, 46 (36), 6899-6902.
29. (a) Luo, Z.; Zhang, Q.; Oderaotoshi, Y.; Curran, D. P., Fluorous mixture synthesis: a fluorous-tagging strategy for the synthesis and separation of mixtures of organic compounds. Science 2001, 291 (5509), 1766-1769; (b) Zhang, Q.; Rivkin, A.; Curran, D. P., Quasiracemic synthesis: concepts and implementation with a fluorous tagging strategy to make both enantiomers of pyridovericin and mappicine. J. Am. Chem. Soc. 2002, 124 (20), 5774-5781; (c) Curran, D. P.; Moura-Letts, G.; Pohlman, M., Solution-phase mixture synthesis with fluorous tagging en route: total synthesis of an eight-member stereoisomer library of passifloricins. Angew. Chem., Int. Ed. Engl. 2006, 45 (15), 2423-2436; (d) Curran, D. P.; Zhang, Q.; Richard, C.; Lu, H.; Gudipati, V.; Wilcox, C. S., Total synthesis of a 28-member stereoisomer library of murisolins. J. Am. Chem. Soc. 2006, 128 (29), 9561-9573.
30. Montanari, V.; Kumar, K., Just add water: a new fluorous capping reagent for facile purification of peptides synthesized on the solid phase. J. Am. Chem. Soc. 2004, 126 (31), 9528-9529.
31. (a) Miura, T.; Goto, K.; Waragai, H.; Matsumoto, H.; Hirose, Y.; Ohmae, M.; Ishida, H. K.; Satoh, A.; Inazu, T., Rapid oligosaccharide synthesis using a fluorous protective group. J. Org. Chem. 2004, 69 (16), 5348-5353; (b) Carrel, F. R.; Geyer, K.; Codee, J. D.; Seeberger, P. H., Oligosaccharide synthesis in microreactors. Org. Lett. 2007, 9 (12), 2285-2288.
32. Mizuno, M.; Goto, K.; Miura, T., Fluorous Glycopeptide Synthesis without Protection of Sugar Hydroxy Groups. Chem. Lett. 2005, 34 (3), 426-427.
33. Pearson, W. H.; Berry, D. A.; Stoy, P.; Jung, K. Y.; Sercel, A. D., Fluorous affinity purification of oligonucleotides. J. Org. Chem. 2005, 70 (18), 7114-7122.
34. Gladysz, J. A.; Curran, D. P., Fluorous chemistry: from biphasic catalysis to a parallel chemical universe and beyond. Tetrahedron 2002, 58 (20), 3823-3825.
35. Jaipuri, F. A.; Pohl, N. L., Toward solution-phase automated iterative synthesis: fluorous-tag assisted solution-phase synthesis of linear and branched mannose oligomers. Org. Biomol. Chem. 2008, 6 (15), 2686-2691.
36. Curran, D. P.; Luo, Z., Fluorous Synthesis with Fewer Fluorines (Light Fluorous Synthesis):  Separation of Tagged from Untagged Products by Solid-Phase Extraction with Fluorous Reverse-Phase Silica Gel. J. Am. Chem. Soc. 1999, 121 (39), 9069-9072.
37. (a) Zhang, W.; Tempest, P., Highly efficient microwave-assisted fluorous Ugi and post-condensation reactions for benzimidazoles and quinoxalinones. Tetrahedron Lett. 2004, 45 (36), 6757-6760; (b) Curran, D. P.; Amatore, M.; Guthrie, D.; Campbell, M.; Go, E.; Luo, Z., Synthesis and Reactions of Fluorous Carbobenzyloxy (FCbz) Derivatives of α-Amino Acids. J. Org. Chem. 2003, 68 (12), 4643-4647; (c) de Visser, P. C.; van Helden, M.; Filippov, D. V.; van der Marel, G. A.; Drijfhout, J. W.; van Boom, J. H.; Noort, D.; Overkleeft, H. S., A novel, base-labile fluorous amine protecting group: synthesis and use as a tag in the purification of synthetic peptides. Tetrahedron Lett. 2003, 44 (50), 9013-9016; (d) Manzoni, L.; Castelli, R., Froc:  A New Fluorous Protective Group for Peptide and Oligosaccharide Synthesis＋. Org. Lett. 2006, 8 (5), 955-957; (e) Villard, A. L.; Warrington, B. H.; Ladlow, M., A fluorous-tagged, acid-labile protecting group for the synthesis of carboxamides and sulfonamides. J. Comb. Chem. 2004, 6 (4), 611-622; (f) Naka, H.; Akagi, Y.; Yamada, K.; Imahori, T.; Kasahara, T.; Kondo, Y., Fluorous Synthesis of Yuehchukene by α-Lithiation of Perfluoroalkyl-Tagged 1-(Arylsulfonyl)indole with Mesityllithium. Eur. J. Org. Chem. 2007, 2007 (28), 4635-4637; (g) Röver, S.; Wipf, P., Synthesis and applications of fluorous silyl protecting groups with improved acid stability. Tetrahedron Lett. 1999, 40 (31), 5667-5670; (h) Dakas, P.-Y.; Barluenga, S.; Totzke, F.; Zirrgiebel, U.; Winssinger, N., Modular Synthesis of Radicicol A and Related Resorcylic Acid Lactones, Potent Kinase Inhibitors. Angew. Chem., Int. Ed. 2007, 46 (36), 6899-6902; (i) Zhang, Q.; Lu, H.; Richard, C.; Curran, D. P., Fluorous Mixture Synthesis of Stereoisomer Libraries:  Total Syntheses of (+)-Murisolin and Fifteen Diastereoisomers. J. Am. Chem. Soc. 2003, 126 (1), 36-37.
38. (a) Cioffi, C. L.; Berlin, M. L.; Herr, R. J., synlett 2004, 5, 841-845; (b) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T., A Highly Efficient Microwave-Assisted Suzuki Coupling Reaction of Aryl Perfluorooctylsulfonates with Boronic Acids. Org. Lett. 2004, 6 (9), 1473-1476; (c) Jing, Y.; Huang, X., Fluorous thiols in oligosaccharide synthesis. Tetrahedron Lett. 2004, 45 (24), 4615-4618; (d) Chen, C. H.-T.; Zhang, W., FluoMar, a Fluorous Version of the Marshall Resin for Solution-Phase Library Synthesis. Org. Lett. 2003, 5 (7), 1015-1017; (e) Fustero, S.; Catalán, S.; Flores, S.; Jiménez, D.; del Pozo, C.; Luis Aceña, J.; Sanz-Cervera, J. F.; Mérida, S., First Fluorous Synthesis of Fluorinated Uracils. QSAR & Comb. Science 2006, 25 (8-9), 753-760; (f) Zhang, W.; Lu, Y., Fluorous Synthesis of Hydantoins and Thiohydantoins. Org. Lett. 2003, 5 (14), 2555-2558; (g) Studer, A.; Jeger, P.; Wipf, P.; Curran, D. P., Fluorous Synthesis:  Fluorous Protocols for the Ugi and Biginelli Multicomponent Condensations. J. Org. Chem. 1997, 62 (9), 2917-2924; (h) Leach, S. G.; Cordier, C. J.; Morton, D.; McKiernan, G. J.; Warriner, S.; Nelson, A., A Fluorous-Tagged Linker from Which Small Molecules Are Released by Ring-Closing Metathesis. J. Org. Chem. 2008, 73 (7), 2753-2759.
39. (a) Zhang, W., Fluorous Synthesis of Disubstituted Pyrimidines. Org. Lett. 2003, 5 (7), 1011-1013; (b) McAllister, L. A.; McCormick, R. A.; Brand, S.; Procter, D. J., A Fluorous-Phase Pummerer Cyclative-Capture Strategy for the Synthesis of Nitrogen Heterocycles. Angew. Chem., Int. Ed. 2005, 44 (3), 452-455; (c) Horhant, D.; Lamer, A.-C. L.; Boustie, J.; Uriac, P.; Gouault, N., Separation of a mixture of paraconic acids from Cetraria islandica (L.) Ach. employing a fluorous tag-catch and release strategy. Tetrahedron Lett. 2007, 48 (34), 6031-6033; (d) Spivey, A. C.; Tseng, C. C.; Hannah, J. P.; Gripton, C. J.; de Fraine, P.; Parr, N. J.; Scicinski, J. J., Light-fluorous safety-catch arylgermanes - exceptionally robust, photochemically activated precursors for biaryl synthesis by Pd(0) catalysed cross-coupling. Chem. Commun. 2007, 43 (28), 2926-2928.
40. Curran, D. P.; Ferritto, R.; Hua, Y., Preparation of a fluorous benzyl protecting group and its use in fluorous synthesis approach to a disaccharide. Tetrahedron Lett. 1998, 39 (28), 4937-4940.
41. Kojima, M.; Nakamura, Y.; Takeuchi, S., A practical fluorous benzylidene acetal protecting group for a quick synthesis of disaccharides. Tetrahedron Lett. 2007, 48 (25), 4431-4436.
42. Ko, K.-S.; Park, G.; Yu, Y.; Pohl, N. L., Protecting-Group-Based Colorimetric Monitoring of Fluorous-Phase and Solid-Phase Synthesis of Oligoglucosamines. Org. Lett. 2008, 10 (23), 5381-5384.
43. Zhang, F.; Zhang, W.; Zhang, Y.; Curran, D. P.; Liu, G., Synthesis and applications of a light-fluorous glycosyl donor. J. Org. Chem. 2009, 74 (6), 2594-2597.
44. Kim, K. S.; Fulse, D. B.; Baek, J. Y.; Lee, B. Y.; Jeon, H. B., Stereoselective direct glycosylation with anomeric hydroxy sugars by activation with phthalic anhydride and trifluoromethanesulfonic anhydride involving glycosyl phthalate intermediates. J. Am. Chem. Soc. 2008, 130 (26), 8537-8547.
45. Huang, X.; Huang, L.; Wang, H.; Ye, X.-S., Iterative One-Pot Synthesis of Oligosaccharides. Angew. Chem. Int. Ed. 2004, 43 (39), 5221-5224.
46. Liang, C.-F.; Yan, M.-C.; Chang, T.-C.; Lin, C.-C., Synthesis of S-Linked α(2→9) Octasialic Acid via Exclusive α S-Glycosidic Bond Formation. J. Am. Chem. Soc. 2009, 131 (9), 3138-3139.
47. Mizuno, M.; Kitazawa, S.; Goto, K., p-Alkoxyphenyl-type heavy fluorous tag for the preparation of carbohydrate units. J. Fluorine Chem. 2008, 129 (10), 955-960.
48. (a) Zhang, Z.; Ollmann, I. R.; Ye, X.-S.; Wischnat, R.; Baasov, T.; Wong, C.-H., Programmable One-Pot Oligosaccharide Synthesis. J. Am. Chem. Soc. 1999, 121 (4), 734-753; (b) Huang, L.; Wang, Z.; Li, X.; Ye, X.-s.; Huang, X., Iterative one-pot syntheses of chitotetroses. Carbohydr. Res. 2006, 341 (10), 1669-1679.
49. (a) Kawakami, H.; Goto, K.; Mizuno, M., Multi-step Synthesis of a Protected Monosaccharide Unit by Iterative Reactions in Microreactors and Fluorous Liquid-phase Extractions. Chem. Lett. 2009, 38 (9), 906-907; (b) Grindley, T. B.; Thangarasa, R., The structures and reactions of stannylene acetals from carbohydrate-derived trans-diols. Part I. In the absence of added nucleophiles. Can. J. Chem. 1989, 68, 1007-1019.
50. Johnsson, R.; Ohlin, M.; Ellervik, U., Reductive openings of benzylidene acetals revisited: a mechanistic scheme for regio- and stereoselectivity. J. Org. Chem. 2010, 75 (23), 8003-8011.
51. (a) Chang, R.; Moquist, P.; Finney, N. S., Chemical synthesis of UDP-4-O-methyl-GlcNAc, a potential chain terminator of chitin synthesis. Carbohydr. Res. 2004, 339 (8), 1531-1536; (b) K. Bock,; I. Lundt,; C. Pedersen, Tetrahedron Lett., 1973, 1037.
52. Wang, Y.; Huang, X.; Zhang, L.-H.; Ye, X.-S., A Four-Component One-Pot Synthesis of α-Gal Pentasaccharide. Org. Lett. 2004, 6 (24), 4415-4417.
53. Tsuboi, T.; Takaguchi, Y.; Tsuboi, S., Novel Photoreaction Using Diphenyl Disulfide Derivatives: Photoinduced Oxidation of Allyl Alcohol. Bull. Chem. Soc. Jpn. 2008, 81 (3), 361-368.
54. DeCollo, T. V.; Lees, W. J., Effects of Aromatic Thiols on Thiol−Disulfide Interchange Reactions That Occur during Protein Folding. J. Org. Chem. 2001, 66 (12), 4244-4249.
55. Srivastava, G.; Hindsgaul, O., Synthesis of Polylactosamine Oligomers by Disaccharide Polymerization. J. Carbohydr. Chem. 1991, 10 (5), 927 - 933.
56. (a) Wang, H.; She, J.; Zhang, L.-H.; Ye, X.-S., Silver(I) Oxide Mediated Selective Monoprotection of Diols in Pyranosides. J. Org. Chem. 2004, 69 (17), 5774-5777; (b) Cumpstey, I.; Chayajarus, K.; Fairbanks, A. J.; Redgrave, A. J.; Seward, C. M. P., Allyl protecting group mediated intramolecular aglycon delivery: optimisation of mixed acetal formation and mechanistic investigation. Tetrahedron: Asymmetry 2004, 15 (20), 3207-3221.
57. Grann Hansen, S.; Skrydstrup, T., Studies Directed to the Synthesis of Oligochitosans – Preparation of Building Blocks and Their Evaluation in Glycosylation Studies. Eur. J. Org. Chem. 2007, 2007 (20), 3392-3401.
58. (a) Beignet, J.; Tiernan, J.; Woo, C. H.; Kariuki, B. M.; Cox, L. R., Stereoselective synthesis of allyl-C-mannosyl compounds: use of a temporary silicon connection in intramolecular allylation strategies with allylsilanes. J. Org. Chem. 2004, 69 (19), 6341-6356; (b) Mayer, T. G.; Schmidt, R. R., Glycosyl Phosphatidylinositol (GPI) Anchor Synthesis Based on Versatile Building Blocks – Total Synthesis of a GPI Anchor of Yeast. Eur. J. Org. Chem. 1999, 1999 (5), 1153-1165; (c) Perlin, A. S., Formation of diastereoisomeric orthoacetates of D-mannose: N.M.R. spectral evidence. Can. J. Chem. 1963, 41 (2), 399-406.