methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzyl-α-D-ribofuranosyl)-α-D-glucopyranoside | 86883-47-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzyl-α-D-ribofuranosyl)-α-D-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzyl-α-D-ribofuranosyl)-D-glucopyranoside；(2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-2-((((2S,3R,4R,5R)-3,4-bis(benzyloxy)-5-((benzyloxy)methyl)tetrahydrofuran-2-yl)oxy)methyl)-6-methoxytetrahydro-2H-pyran；(2R,3R,4S,5R,6S)-2-[[(2S,3R,4R,5R)-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)oxolan-2-yl]oxymethyl]-6-methoxy-3,4,5-tris(phenylmethoxy)oxane
• CAS: 86883-47-8
• 化学式: C₅₄H₅₈O₁₀
• 分子量: 867.049
• InChiKey: PBQRGXCYBBCRLI-HNGZDGACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  64
• 可旋转键数：
  23
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  92.3
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  2,3,5-tri-O-benzyl-α-D-ribofuranosyl fluoride 在 molecular sieve 、 三氟化硼乙醚 、 triphenylmethyl perchlorate 、 tin(ll) chloride 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(2,3,5-tri-O-benzyl-α-D-ribofuranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  使用呋喃糖基氟化物立体选择性合成 1,2-顺式-呋喃糖苷

  摘要：

  在氯化亚锡和高氯酸三苯甲基酯的存在下，通过 β-呋喃核糖基氟和醇的反应，以高产率立体选择性地合成 1,2-顺式-呋喃核糖苷。在类似条件下，α-阿拉伯呋喃糖基氟与胆甾醇反应主要生成1,2-顺式-阿拉伯呋喃糖苷。

  DOI：

  10.1246/cl.1983.935

文献信息

• An Efficient Glycosylation Reaction of 1-Hydroxy Sugars with Various Nucleophiles Using A Catalytic Amount of Activator and Hexamethyldisiloxane
  作者：Teruaki Mukaiyama、Koki Matsubara、Miyuki Hora

  DOI：10.1055/s-1994-25695

  日期：——

  In the presence of hexamethyldisiloxane and anhydrous calcium sulfate, a catalytic amount of activator such as tin(II) trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate , lanthanum trifluoromethanesulfonate or tin(II) chloride smoothly promotes the glycosylation reactions between 1-hydroxy sugars and free alcohols, electron-rich aromatic compounds or silylated nucleophiles to produce various O -, C - or N - glycosides stereoselectively in high yields. In the case of oxygen or nitrogen nucleophiles, β-ribosides are formed, except that α-ribosides are obtained predominantly in the presence of lithium perchlorate. In the case of carbon nucleophiles such as electron-rich aromatic compounds or silyl enol ethers derived from carbonyl compounds, perfect β-selectivity is shown either in the the presence or absence of lithium perchlorate. Further, pyranosyl substrates such as glucose or galactose afford the corresponding α-anomers, except with electron-rich aromatic compounds.

  在六甲基二硅氧烷和无水硫酸钙的存在下，以催化量的活化剂（如二氟三氟甲磺酸锡、三氟三氟甲磺酸镱、三氟三氟甲磺酸镧或二氯化锡）顺利促进1-羟基糖与自由醇、富电子芳香化合物或硅化亲核试剂之间的糖基化反应，高产率地选择性合成各种O-、C-或N-糖苷。对于氧或氮亲核试剂，主要生成β-核糖苷，但在高氯酸锂存在下主要得到α-核糖苷。对于碳亲核试剂（如富电子芳香化合物或来自羰基化合物的硅基烯醇醚），无论在高氯酸锂存在或不存在下，均表现出完全的β-选择性。此外，吡喃糖基底物（如葡萄糖或半乳糖）主要生成相应的α-异构体，但对于富电子芳香化合物则例外。
• Halogen-bond-assisted radical activation of glycosyl donors enables mild and stereoconvergent 1,2-cis-glycosylation
  作者：Chen Zhang、Hao Zuo、Ga Young Lee、Yike Zou、Qiu-Di Dang、K. N. Houk、Dawen Niu

  DOI：10.1038/s41557-022-00918-z

  日期：2022.6

  2-cis-glycosylation without using metals, strong (Lewis) acids, elaborate catalysts or labile substrates. Our method operates by a unique mechanism: it activates glycosyl donors through a radical cascade rather than the conventional acid-promoted, ionic process. As elucidated by computational and experimental studies, the allyl glycosyl sulfones (as donors) form halogen bond complexes with perfluoroalkyl iodides, which—merely

  碳水化合物的化学已有 100 多年的历史，但仍然非常需要简单、立体选择性和高效的糖基化方法来促进各学科对糖的研究。在这里，我们报告了 1,2- cis-糖基化不使用金属、强（路易斯）酸、精细催化剂或不稳定底物。我们的方法通过一种独特的机制运作：它通过自由基级联激活糖基供体，而不是传统的酸促进离子过程。正如计算和实验研究所阐明的，烯丙基糖基砜（作为供体）与全氟烷基碘形成卤素键复合物，仅通过可见光照射，通过自由基中间体断裂，得到亲电子糖基碘。各种亲核试剂的原位捕获以立体收敛的方式提供具有挑战性的 1,2-顺式-糖苷。这种不含金属和酸的反应对官能团表现出显着的耐受性。高立体选择性适用于广泛的供体。该研究表明，简单的 C2-烷氧基可以作为构建 1,2-顺式-糖苷键的有效导向基团。
• An Efficient Method for the Stereoselective Synthesis of<i>β</i>-D- and<i>α</i>-D-Ribofuranosides from 2,3,5-Tri-<i>O</i>-benzyl-D-ribofuranose by the Use of [Catecholato(2−)-<i>O</i>,<i>O</i>′]oxotitanium and Trifluoromethanesulfonic Anhydride
  作者：Shinji Suda、Teruaki Mukaiyama

  DOI：10.1246/bcsj.66.1211

  日期：1993.4

  β-d-Ribofuranosides are stereoselectively synthesized in high yields directly from 2,3,5-tri-O-benzyl-d-ribofuranose and trimethylsilylated nucleophiles by the use of [catecholato(2−)-O,O′ ]oxotitanium and trifluoromethanesulfonic anhydride, while α-d-ribofuranosides are prepared predominantly in high yields in the coexistence of lithium perchlorate.

  通过使用[邻苯二酚（2-）-O、O′ ]氧钛和三氟甲磺酸酐，而 α-d-ribofuranosides 则主要是在高氯酸锂的作用下以高产率制备的。
• Stereoselective Glycosylation Reaction Starting from 1-O-Trimethylsilyl Sugars by Using Diphenyltin Sulfide and a Catalytic Amount of Active Acidic Species
  作者：Teruaki Mukaiyama、Koki Matsubara

  DOI：10.1246/cl.1992.1041

  日期：1992.6

  1,2-trans-Ribofuranosides are stereoselectively synthesized from 1-O-trimethylsilyl ribofuranose and trimethylsilyl ethers in the presence of a catalytic amount of Me3SiOTf using Ph2Sn=S as an additive, while 1,2-cis-ribofuranosides and 1,2-cis-glucopyranosides are prepared predominantly in the coexistence of LiClO4 in the above reaction.

  在催化量的 Me3SiOTf 存在下，使用 Ph2Sn=S 作为添加剂，从 1-O-三甲基甲硅烷基呋喃核糖和三甲基甲硅烷基醚立体选择性地合成 1,2-反式-呋喃核糖苷，而 1,2-顺式-呋喃核糖苷和 1,2-在上述反应中，顺式吡喃葡萄糖苷主要在 LiClO4 共存下制备。
• Stereoselective Syntheses of<i>α</i>-D- and<i>β</i>-D-Ribofuranosides Catalyzed by the Combined Use of Silver Salts and Their Partners
  作者：Naoyuki Shimomura、Teruaki Mukaiyama

  DOI：10.1246/bcsj.67.2532

  日期：1994.9

  α-d-Ribofuranosides are stereoselectively synthesized in high yields from 2,3,5-tri-O-benzyl-1-O-iodoacetyl-d-ribofuranose (1) and trimethylsilylated nucleophiles by the use of silver salts in the coexistence of 3 molar amounts of lithium perchlorate, while β-d-ribofuranosides are prepared predominantly in high yields by the reaction of 1 and trimethylsilylated nucleophiles or 2,3,5-tri-O-benzyl-d-ribofuranose and free alcohols by using [diphenyltin sulfide/silver salt] or [Lawesson’s reagent/silver salt] combined catalyst system.

  α-d-核呋喃糖苷是由 2,3,5-三-O-苄基-1-O-碘乙酰-d-核呋喃糖（1）和三甲基硅烷基化的亲核物通过使用银盐与 3 摩尔量的高氯酸锂共存进行立体选择性高产率合成的、而使用[二苯基硫化锡/银盐]或[Lawesson 试剂/银盐]组合催化剂体系，通过 1 和三甲基硅烷化亲核物或 2,3,5-三-O-苄基-d-呋喃三糖与游离醇的反应，主要可以高产率制备出 β-d-呋喃核苷。