Muthana Saddam, Yu Hai, Cao Hongzhi, Cheng Jiansong, Chen Xi
Department of Chemistry, One Shields Avenue, University of California, Davis, California 95616, USA.
J Org Chem. 2009 Apr 17;74(8):2928-36. doi: 10.1021/jo8027856.
A novel and highly efficient chemoenzymatic method has been developed for the preparation of structurally defined macrocyclic oligosaccharides of varied sizes. This method involves chemical or chemoenzymatic synthesis of oligosaccharides containing a galactose at the nonreducing end and a propargyl group at the reducing end as sialyltransferase acceptors. Introducing an azido-containing sialic acid to the nonreducing end of the galactosides through a sialyltransferase-catalyzed enzymatic reaction followed by copper(I)-catalyzed Huisgen's 1,3-dipolar cycloaddition of alkyne and azide provides size-defined macrocyclic carbohydrates. The produced negatively charged macrocycles have high solubility in water and interact with hydrophobic small molecules in a size-dependent manner.
已开发出一种新颖且高效的化学酶法，用于制备结构明确、大小各异的大环寡糖。该方法包括化学合成或化学酶法合成在非还原端含有半乳糖且在还原端含有炔丙基的寡糖，作为唾液酸转移酶的受体。通过唾液酸转移酶催化的酶促反应，将含叠氮基的唾液酸引入半乳糖苷的非还原端，随后通过铜（I）催化的炔烃与叠氮化物的休斯根1,3 -偶极环加成反应，得到大小确定的大环碳水化合物。所产生的带负电荷的大环化合物在水中具有高溶解度，并以大小依赖的方式与疏水性小分子相互作用。
