標題: 壹、溶劑參與效應醣基化反應一鍋化策略; 貳、2-疊氮-2去氧醣予體合成天然寡醣
(1)Solvent Participating One-pot Glycosylation, (2)Oligosaccharides Synthesis Using 2-Azido-2-Deoxy- Glycopyranosyl Donors
作者: 顏鈺芳
Yen, Yu-Fang
蒙國光
Mong, Kwok-Kong T.
應用化學系碩博士班
關鍵字: 醣質化反應;腈類溶劑;胺糖;一鍋醣質化反應;glycosylation;nitrile solvent;amino sugar;one-pot glycosylation
公開日期: 2010
摘要: 本論文分為兩大部分: 1. 在建構 beta-選擇性醣苷鍵策略中,溶劑參與效應一鍋化醣質化反應 (SPOG) 已被普遍使用在低濃度腈類混和溶劑反應系統中。這種策略可在一鍋化策略的情況下控制生成良好的 立體選擇性。同時,我們更衍生應用於正交醣基化反應策略,將醣基磷酸酯予體及硫醣受體搭配,經由一鍋化的方式合成產率極佳的寡醣分子。 2. 葡萄糖胺是一種和人類息息相關重要醣分子之一,一般含有胺基或是乙醯基保護的胺基。而三疊氮 (azido,N3) 保護基可在溫和的情況下被還原去保護,並且因為三疊氮保護基缺乏鄰助基效應一般常被用來使用製備beta 醣苷鍵。我們發展了具備高產率及良好的1,2-反式 beta-選擇性的溶劑鄰助基策略,使用在2-三疊氮-去氧葡萄糖胺予體上,並且成功的得到與生物有關的F1-apha前驅物以及(1,6)-beta葡萄糖胺寡醣鏈。
This thesis is divide into two parts: 1. Solvent participating one-pot glycosylation (SPOG) strategy was developed on the base of low concentration beta-selective glycosylation method. This strategy enables the control of stereochemistry in one-pot glycosylations through solvent addition. Meanwhile, further application of the low concentratnion glycosylation (LCG) to orthogonal glycosylation strategy is explored. Combining glycosyl phosphates and thioglycosides, oligosaccharides could be synthesized in a one-pot manner to furnish in good yield and excellent stereoselectivity. 2. Glucosamine is one of the major amino sugars present in human-related oligosaccharides, which contain an amino group (or acetamido) at the C-2 position. The azido function can readily be reduced to amine under mild conditions. Due to the non-participation nature, 2-azido-2-deoxy glycosyl donors are mandatory substrates for construction of 1,2-cis apha-glycosidic bond under specific reaction condition We developed a high-yielding and stereocontolled construction of 1,2-trans-beta-glycosidic linkages with 2-azido-2- deoxy glycopyranosyl donors using the solvent participated one-pot glycosylation strategy. We successfully prepared some biological relevant oligosaccharide targets such as F1-apha precursor trisaccharide, and beta-(1,6) glucosamine.
URI: http://140.113.39.130/cdrfb3/record/nctu/#GT079825527
http://hdl.handle.net/11536/47616
Appears in Collections:Thesis