CN119490545A 构建2-硫代-2-脱氧糖苷键的方法 （江西师范大学）

代2脱氧糖苷键的方法。所述方法使2位含邻炔基苯甲酸酯基团的糖苷化给体和醇或酚受体233.根据权利要求1所述的方法，其特征在于3所述如式I所示的糖苷化给体和有机溶剂的摩尔体积比为0.001～04构建2硫代2脱氧糖苷键的方法[0003]目前构建2一脱氧糖苷键的方法主要可以分为以下5种，直接合成(direct成(denovosynthesis)和异头端烷基化(anomerica用DAST引发的1,2硫苷迁移实现了2脱氧糖苷键的立体选择性构建(参考现有技术文献用鼠李糖2,3位原酸酯硫苷实现了2一硫代脱氧鼠李糖苷的立体选择性构建(参考现有技术[0006]2005年，Lipt5喃型糖以外，该方法还可用于2_脱氧吡喃型糖如2_脱氧鼠李糖糖苷键的构建(参考现有技Synthesis.Chem.Rev.2topreventaglycontransferofthioglycosides.J.Am.Chem.Soc.2006,128(35),11612_9.[0010]现有技术文献3：Nicolaou,K.C.；Ladduwahetty,T.；RandavanBoom,J.H.,Stereospecific1,2_ethyl(phenyl)thiogroupdeoxyglycosides.TetrahedronLett.199βglycosidesbasedona1,2_ethyl(phenyl)thiogroupmigration.Tetrahedronstereoselectivesynthesisof2_S_ethyl(phenyl)_2_deoxy_beta_glycosides,readyprecursorsto2_deoxy_beta_glycosides.TetrahedronLett.2002_deoxy_beta_glycosidesusingphenyl2,3_O_thionocarbonyl_1_thioglycosidedonorsvia1,2_migrationandconcurrentglycosidation.Org.Lett.2001,3(3),377_379.theSaccharideAssembly.Synthesis_StuttgGlycosylazidesofsugar2_sulfonicacids.TetrahedronLett.2005,46(31),5191_5194.6of2deoxy2thiophenylglucosylazidesthrough1,2thiomigrationofthiophenyldeoxyfuranosidesfrom2,3anhydrofuranosylthioglycosides.Org.Lett.2007,92289.7选4选为1.5:1；所述如式I所示的糖苷化给体和催化剂的摩尔比为1:0.1～1:0.5，优选为1:8SMp表示对甲氧基苯硫基；9完全反应后，将其混合物真空浓缩，用硅胶纯化(PE:EA＝6:1)，得到化合物I1(210mg,0.83(m,4H)；[0064]HRMS(ESI)calcdforC46H45O7S[M+H]+741.28860,found741.28754.[0068]式I4所示化合物的产率为82其表征数据如[0071]13CNMR(100M[0072]HRMS(ESI)calcdforC39H34O8S[M+H]+663.20527,found663.20548.[0075]式I5所示化合物的产率为92其表征数据如_2.2(c1.0,CHCl3)；80.3,74.7,73.7,72.2,70.8,68.7,[0079]HRMS(ESI)calcdforC35H34O7SNa[M+Na]+621.19230,found621.19261.[0082]式I6所示化合物的产率为76其表征数据[0085]13CNMR(100M[0086]HRMS(ESI)calcdforC46H38O10S[M+Na]+805.2088,found805.20834.[0089]式I7所示化合物的产率为92其表征数据如128.6,128.5,128.4,128.2(2C),128.0(2C),1279.8,78.0,75.4,75.3,74.8,73.6,72[0094]式I8所示化合物的产率为85其表征数据)；[0098]HRMS(ESI)calcdforC39H38O6S[M+K]+673.202621,found673.202881.[0101]将给体化合物I1(104mg,0.15mmol)与受体6_OH_2,3,4_三苄基葡萄糖甲苷(47mg,Et3N淬灭反应，抽滤除去体系中的分子筛后减压浓缩，柱色谱分离得到化合物P1(90mg，3H)；[0103]13CNMR(100M114.6,100.3,97.8,82.2,80.1,78.3,77.6,75.9,75.1,75.0,74.969.8,69.1,65.8,55.4,55.2,54.1.[0107]化合物P3的产率为88其表征数据如下：[0109]13CNMR(100M122.5,114.6,96.6,82.8,78.9,77.4,75.2,75.0,73.3,72.3,71.6,69.3,66.0,55.5,55.4,28.8,27.7,26.0,23.7,23.5,23.1,21.9,18.3,[0112]化合物P6的产率为99其表征数据如_28.3(c1.0,CHCl3)；[0115]13CNMR(10074.8,73.7,73.6,73.5,69.8,68.9,68.6[0116]HRMS(ESI)calcdforC62H66O11[0119]化合物P7的产率为87其表征数据_21.2(c1.0,CHCl3)；[0122]13CNMR(100M75.1,75.1,73.7,71.8,69.1,60.8,58.8,56.2,55.4,[0123]HRMS(ESI)calcdforC56H56O13S[M+H]+969.35199,found969.35193.[0126]化合物P9的产率为98其表征数据如下：[0129]13CNMR(100M103.0,98.1,85.0,82.8,82.0,80.1,77.6,76.1,75.7,75.3,75.0,73.5,70.9,70.4,67.4,[0130]HRMS(ESI)calcdforC55H60O10SNa[M+Na]+935.3805,found935.3784.[0133]化合物P10的产率为99其表征数据如127.3,114.4,102.5,97.8,85.2,83.4,81.7,80.6,76.3,7[0137]HRMS(ESI)calcdforC55H60O10[0140]化合物P11的产率为87其表征数据[0143]13CNMR(100M74.5,73.5,69.6,58.8,55.5,[0144]HRMS(ESI)calcdforC44H5[0147]化合物P12的产率为80其表征数据)；0.91_0.81(m,2H)；[0150]13CNMR(100M128.5,128.1,128.0,127.9,127.8,127.7,125.5,125.0,114.4,108.7,102.2,83.1,79.76.0,75.0,74.9,73.7,73.6,69.1,57.2,55.5,41.2,30.7,[0151]HRMS(ESI)calcdforC44H56O6S[M+NH4]+724.36719,found724.36673.[0154]化合物P13的产率为99其表征数据如_2.5(c1.0,CHCl3)；[0157]13CNMR(100M68.7,68.5,6