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Hydrophobically Assisted Switching Phase Synthesis:  The Flexible Combination of Solid-Phase and Solution-Phase Reactions Employed for Oligosaccharide Preparation

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Leibniz Institute for Molecular Pharmacology (FMP), 13125 Berlin, Germany, Institute for Chemistry, Organic Chemistry, Free University of Berlin, 14195 Berlin, Germany, and Institute for Organic Chemistry, Eberhard-Karls-University Tübingen, 72076 Tübingen, Germany
Cite this: J. Am. Chem. Soc. 2005, 127, 20, 7296–7297
Publication Date (Web):April 28, 2005
https://doi.org/10.1021/ja051737x
Copyright © 2005 American Chemical Society

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    Abstract

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    Hydrophobically assisted switching phase (HASP) synthesis is a concept that allows the choice between the advantages of solid-supported chemistry and those of solution-phase synthesis. Starting from the examination of adsorption and desorption properties of hydrophobic molecules to and from reversed-phase silica, we designed a dilipid as a quantitative and fully reversible HASP anchor, permitting final product release. The utility of this new tool in synthetic organic chemistry was demonstrated on oligosaccharide preparation. The synthesis of a pentarhamnoside was accomplished by repetitive glycosylation reactions. Glycosylations were conducted preferably in solution, whereas all protecting group manipulations were performed on solid support. Without the need for chromatographic purification of intermediates, the HASP system furnished the final product after 12 linear steps with average yields of 94% per step at a scale of 0.1 mmol, thus overcoming several of the limitations encountered in the solid-phase synthesis of complex carbohydrates.

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     Leibniz Institute for Molecular Pharmacology.

     University of Tübingen.

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    15. Sébastien Vidal, Peter G. Goekjian. Protecting Groups at the Secondary Positions of Carbohydrates. 2019, 69-108. https://doi.org/10.1002/9783527697014.ch3
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    17. Yunhe Wang, Shuai Meng, Tingting Yue, Shuchun Li, Zhongjun Li. The rapid assembling of oligosaccharides by the developed HASP strategy. Chinese Chemical Letters 2018, 29 (1) , 69-72. https://doi.org/10.1016/j.cclet.2017.09.045
    18. Yong-Hai Chai, Ying-Le Feng, Jing-Jing Wu, Chu-Qiao Deng, Ai-Yun Liu, Qi Zhang. Recyclable benzyl-type fluorous tags: Preparation and application in oligosaccharide synthesis. Chinese Chemical Letters 2017, 28 (8) , 1693-1700. https://doi.org/10.1016/j.cclet.2017.06.020
    19. Felix Müller, Stefan Hönzke, Wulf-Ole Luthardt, Ee Lin Wong, Michael Unbehauen, Jörg Bauer, Rainer Haag, Sarah Hedtrich, Eckart Rühl, Jörg Rademann. Rhamnolipids form drug-loaded nanoparticles for dermal drug delivery. European Journal of Pharmaceutics and Biopharmaceutics 2017, 116 , 31-37. https://doi.org/10.1016/j.ejpb.2016.12.013
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    21. Xin‐Shan Ye, Weigang Lu. GENERAL ASPECTS IN O‐GLYCOSIDIC BOND FORMATION. 2016, 69-95. https://doi.org/10.1002/9781119006435.ch3
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    32. . Jörg Rademann. Angewandte Chemie 2009, 9382-9382. https://doi.org/10.1002/ange.200905149
    33. . Jörg Rademann. Angewandte Chemie International Edition 2009, 9218-9218. https://doi.org/10.1002/anie.200905149
    34. Shankar D. Markad, Richard R. Schmidt. Temporary Carbohydrate Diol Protection with Ester Groups – Orthogonality under Solid‐Phase Oligosaccharide Synthesis Conditions. European Journal of Organic Chemistry 2009, 2009 (29) , 5002-5011. https://doi.org/10.1002/ejoc.200900627
    35. Lourdes Encinas, Jose Luis Chiara. Lipophilic Thioglycosides for the Solution‐Phase Synthesis of Oligosaccharides Using Biphasic Liquid‐Liquid Separation. European Journal of Organic Chemistry 2009, 2009 (13) , 2163-2173. https://doi.org/10.1002/ejoc.200900081
    36. Xiangming Zhu, Richard R. Schmidt. Neue Prinzipien für die Bildung von glycosidischen Bindungen. Angewandte Chemie 2009, 121 (11) , 1932-1967. https://doi.org/10.1002/ange.200802036
    37. Xiangming Zhu, Richard R. Schmidt. New Principles for Glycoside‐Bond Formation. Angewandte Chemie International Edition 2009, 48 (11) , 1900-1934. https://doi.org/10.1002/anie.200802036
    38. James T. Smoot, Alexei V. Demchenko. Chapter 5 Oligosaccharide Synthesis: From Conventional Methods to Modern Expeditious Strategies. 2009, 161-250. https://doi.org/10.1016/S0065-2318(09)00005-5
    39. Feng Cai, Baolin Wu, David Crich. Chapter 6 Stereocontrolled Synthesis of Mannans and Rhamnans. 2009, 251-309. https://doi.org/10.1016/S0065-2318(09)00006-7
    40. Minoru Izumi, Ritsu Okamoto, Mizuho Sato, Shuhei Nakajima, Naomichi Baba, Koichi Fukase. A New Catch-and-release Purification Method Using a Levulinyl Group as a Tag and Its Application to Oligosaccharide Synthesis. Chemistry Letters 2008, 37 (10) , 1030-1031. https://doi.org/10.1246/cl.2008.1030
    41. Gisun Park, Kwang-Seuk Ko, Aleksandra Zakharova, Nicola L. Pohl. Mono- vs. di-fluorous-tagged glucosamines for iterative oligosaccharide synthesis. Journal of Fluorine Chemistry 2008, 129 (10) , 978-982. https://doi.org/10.1016/j.jfluchem.2008.05.001
    42. Nicola L. Pohl. Perfluorierte Marker als Ankergruppen für Mikroarrays. Angewandte Chemie 2008, 120 (21) , 3930-3932. https://doi.org/10.1002/ange.200704801
    43. Nicola L. Pohl. Fluorous Tags Catching on Microarrays. Angewandte Chemie International Edition 2008, 47 (21) , 3868-3870. https://doi.org/10.1002/anie.200704801
    44. Richard R. Schmidt, Xiangming Zhu. Glycosyl Trichloroacetimidates. 2008, 451-524. https://doi.org/10.1007/978-3-540-30429-6_11
    45. Katsunori Tanaka, Koichi Fukase. Polymer-Supported and Tag-Assisted Methods in Oligosaccharide Synthesis. 2008, 1241-1277. https://doi.org/10.1007/978-3-540-30429-6_29
    46. Shokaku Kim, Ai Tsuruyama, Akihiro Ohmori, Kazuhiro Chiba. Solution-phase oligosaccharide synthesis in a cycloalkane-based thermomorphic system. Chemical Communications 2008, 93 (15) , 1816. https://doi.org/10.1039/b717446b
    47. Firoz A. Jaipuri, Nicola L. Pohl. Toward solution-phase automated iterative synthesis: fluorous-tag assisted solution-phase synthesis of linear and branched mannose oligomers. Organic & Biomolecular Chemistry 2008, 6 (15) , 2686. https://doi.org/10.1039/b803451f
    48. Y. Ito, S. Manabe. Polymer-Supported Oligosaccharide Synthesis. 2007, 335-378. https://doi.org/10.1016/B978-044451967-2/00010-6
    49. Shino Manabe, Akiharu Ueki, Yukishige Ito. Polymer-supported oligosaccharide synthesis using ultrafiltration methodology. Chemical Communications 2007, 102 (35) , 3673. https://doi.org/10.1039/b705324j
    50. Takuro Ako, Shusaku Daikoku, Isao Ohtsuka, Rumiko Kato, Osamu Kanie. A Method of Orthogonal Oligosaccharide Synthesis Leading to a Combinatorial Library Based on Stationary Solid‐Phase Reaction. Chemistry – An Asian Journal 2006, 1 (6) , 798-813. https://doi.org/10.1002/asia.200600210
    51. Jörg Howe, Jörg Bauer, Jörg Andrä, Andra B. Schromm, Martin Ernst, Manfred Rössle, Ulrich Zähringer, Jörg Rademann, Klaus Brandenburg. Biophysical characterization of synthetic rhamnolipids. The FEBS Journal 2006, 273 (22) , 5101-5112. https://doi.org/10.1111/j.1742-4658.2006.05507.x
    52. Jörg Bauer, Klaus Brandenburg, Ulrich Zähringer, Jörg Rademann. Chemical Synthesis of a Glycolipid Library by a Solid‐Phase Strategy Allows Elucidation of the Structural Specificity of Immunostimulation by Rhamnolipids. Chemistry – A European Journal 2006, 12 (27) , 7116-7124. https://doi.org/10.1002/chem.200600482
    53. Frank Würthner, Carsten Tschierske, Anke Krüger, Klaus Ditrich, Roland Pfau, Henning Priepke, Rolf Breinbauer, Hans-Achim Wagenknecht, Gerald Dräger, Andreas Kirschning, Norbert Sewald, Uwe Beifuss, Mathias O. Senge, Thomas J. J. Müller, Peter R. Schreiner, Ruth Gschwind, Bernd F. Straub, Kilian Muñiz, Martin Oestreich, Jörg Pietruszka, Thomas Lindel, Roderich Süßmuth, Philippe Bisel, Michael Müller, Elmar Weinhold, Andres Jäschke, Markus Albrecht, Thorsten Bach, Götz Bucher, Heinrich Heydt, Jens Hartung. Organische Chemie 2005. Nachrichten aus der Chemie 2006, 54 (3) , 241-264. https://doi.org/10.1002/nadc.20060540309
    54. Simon Jonke, Ke‐gang Liu, Richard R. Schmidt. Solid‐Phase Oligosaccharide Synthesis of a Small Library of N‐Glycans. Chemistry – A European Journal 2006, 12 (4) , 1274-1290. https://doi.org/10.1002/chem.200500707
    55. Eric Assen B. Kantchev, Scott J. Bader, Jon R. Parquette. Oligosaccharide synthesis on a soluble, hyperbranched polymer support via thioglycoside activation. Tetrahedron 2005, 61 (35) , 8329-8338. https://doi.org/10.1016/j.tet.2005.06.101
    56. N.K. Terrett. Combinatorial Chemistry Online. Combinatorial Chemistry - an Online Journal 2005, 7 (7) , 29-32. https://doi.org/10.1016/j.comche.2005.06.001

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