2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-glucopyranosyl trichloroacetimidate | 858525-75-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-glucopyranosyl trichloroacetimidate
• 英文别名: Bz(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(a)-O-C(NH)CCl3；[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] benzoate
• CAS: 858525-75-4
• 化学式: C₃₆H₃₄Cl₃NO₇
• 分子量: 699.027
• InChiKey: AHWNPSJPXORJSA-XDURGXAYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-glucopyranosyl trichloroacetimidate 在 palladium hydroxide - carbon 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 氢气 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  Highly β-Selective and Direct Formation of 2-O-Glycosylated Glucosides by Ring Restriction into Twist-Boat

  摘要：

  Three disaccharide donors, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl-beta- (D)- xylopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl- alpha- (L)- rhamnopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, and ethyl 2- O( 2,3,4,6- tetrakis- O- tert- butyldimethylsilyl-beta- (D)- glucopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-(beta)- (D)- glucopyranoside, produced a highly beta- selective glycosidation up to alpha/beta = 2/ 98 using MeOTf as the activator and 2,6- lutidine as an additive. The ring conformations of the glucose part in these disaccharide donors were all restricted to S-3(1), and the conformation would lead to the stereoselectivity.

  DOI：

  10.1021/ol070720b
• 作为产物：
  描述：

  三氯乙腈 、 2-O-benzoyl-3,4,6-tri-O-benzyl-D-glucopyranose 在 caesium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以94%的产率得到2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Highly β-Selective and Direct Formation of 2-O-Glycosylated Glucosides by Ring Restriction into Twist-Boat

  摘要：

  Three disaccharide donors, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl-beta- (D)- xylopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, ethyl 2- O- ( 2,3,4- tris- O- tert- butyldimethylsilyl- alpha- (L)- rhamnopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-beta- (D)- glucopyranoside, and ethyl 2- O( 2,3,4,6- tetrakis- O- tert- butyldimethylsilyl-beta- (D)- glucopyranosyl)- 3,4,6- tris- O- tert- butyldimethylsilyl- 1- thio-(beta)- (D)- glucopyranoside, produced a highly beta- selective glycosidation up to alpha/beta = 2/ 98 using MeOTf as the activator and 2,6- lutidine as an additive. The ring conformations of the glucose part in these disaccharide donors were all restricted to S-3(1), and the conformation would lead to the stereoselectivity.

  DOI：

  10.1021/ol070720b

文献信息

• Tris(pentafluorophenyl)borane-Promoted Stereoselective Glycosylation with Glycosyl Trichloroacetimidates under Mild Conditions
  作者：Kunj Bihari Mishra、Adesh Kumar Singh、Jeyakumar Kandasamy

  DOI：10.1021/acs.joc.8b00215

  日期：2018.4.6

  Tris(pentafluorophenyl)borane-promoted stereoselective glycosylation with trichloroacetimidate glycosyl donors is described. The reactions proceed efficiently with a wide range of acceptors, from sugar to nonsugar, under mild conditions in the presence of a catalytic amount of B(C6F5)3. The perbenzylated glucosyl α-imidate provides β-selective glycosides in 70–92% yields.

  描述了用三氯乙酰亚胺酸酯糖基供体的三（五氟苯基）硼烷促进的立体选择性糖基化。在催化量的B（C 6 F 5）3存在下，在温和条件下，反应可利用各种受体（从糖到非糖）有效地进行。过苄基化的葡萄糖基α-亚氨酸酯以70-92％的产率提供β-选择性糖苷。
• Photo-induced glycosylation using reusable organophotoacids
  作者：Ryosuke Iwata、Kanjiro Uda、Daisuke Takahashi、Kazunobu Toshima

  DOI：10.1039/c4cc04753b

  日期：——

  The glycosylation reactions of glycosyl trichloroacetimidates and several alcohols using an organophotoacid as an activator under photoirradiation proceeded smoothly to give the corresponding glycosides in high yields.

  糖基三氯乙酰亚胺和几种醇的糖基化反应，在光照条件下使用有机光酸作为活化剂进行，顺利进行，产率较高地得到相应的糖苷。
• Dimethylthexylsilyl 2-acetamido-3-O-allyl-2-deoxy-6-O-(4-methoxybenzyl)-β-d-glucopyranoside, dimethylthexylsilyl 3,4,6-tri-O-benzyl-β-d-mannopyranosyl-(1→4)-2-acetamido-3-O-allyl-2-deoxy-6-O-(4-methoxybenzyl)-β-d-glucopyranoside, and dimethylthexylsilyl 2-O-(benzylsulfonyl)-3,4,6-tri-O-benzyl-β-d-mannopyranosyl-(1→4)-2-acetamido-3-O-allyl-2-deoxy-6-O-(4-methoxybenzyl)-β-d-glucopyranoside: synthesis of authentic samples
  作者：David Crich、Ming Li、Prasanna Jayalath

  DOI：10.1016/j.carres.2008.10.007

  日期：2009.1

  Dimethylthexylsilyl 2-acetamido-3-O-allyl-2-deoxy-6-O-(4-methoxybenzyl)-beta-D-glucopyranoside was prepared by reduction of the corresponding 4,6-O-(4-methoxybenzylidene) acetal with sodium cyanoborohydride and trifluoroacetic acid. This alcohol was coupled to 2-O-benzoyl-3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl trichloroacetimidate to give a beta-glucoside that was converted to dimethylthexylsilyl

  通过将相应的4,6-O-（4-甲氧基亚苄基）乙缩醛还原为二甲基甲氧基甲硅烷基2-乙酰氨基-3-O-烯丙基-2-脱氧-6-O-（4-甲氧基苄基）-β-D-吡喃葡萄糖苷。氰基硼氢化钠和三氟乙酸。将该醇与2-O-苯甲酰基-3,4,6-三-O-苄基-α-D-吡喃葡萄糖基三氯乙酰亚胺酸酯偶合，得到β-葡糖苷，其被转化为二甲基甲硅烷基甲硅烷基3,4,6-三-O-苄基-β-D-甘露吡喃糖基-（1→4）-2-乙酰胺基-3-O-烯丙基-2-脱氧-6-O-（4-甲氧基苄基）-β-D-吡喃葡萄糖苷马丁氧化，和硼氢化钠还原。然后进行磺酰化得到二甲基甲硅烷基甲硅烷基2-O-（苄基磺酰基）-3,4,6-三-O-苄基-β-D-甘露吡喃糖基-（1→4）-2-乙酰胺基-3-O-烯丙基-2-脱氧-6-O-（4-甲氧基苄基）-β-D-吡喃葡萄糖苷。
• Photo-induced glycosylation using a diaryldisulfide as an organo-Lewis photoacid catalyst
  作者：Naoto Iibuchi、Takahiro Eto、Manabu Aoyagi、Reiji Kurinami、Hayato Sakai、Taku Hasobe、Daisuke Takahashi、Kazunobu Toshima

  DOI：10.1039/c9ob02674f

  日期：——

  Photo-induced glycosylations of several acceptors with trichloroacetimidate donors using bis(2-naphthyl)disulfide as an organo-Lewis photoacid (LPA) catalyst proceeded effectively to give the corresponding glycosides in good to high yields.

  几种受体与三氯乙酰亚胺供体进行光诱导糖基化反应，使用双(2-萘基)二硫化物作为有机路易斯光酸（LPA）催化剂，反应高效进行，得到相应的糖苷产率较高。
• [EN] SAPONIN-BASED VACCINE ADJUVANTS<br/>[FR] ADJUVANTS DE VACCIN À BASE DE SAPONINES
  申请人：UAB RES FOUND

  公开号：WO2019183159A1

  公开（公告）日：2019-09-26

  Provided are variants of saponins that are found in Quillaja saponaria (QS) Molina tree bark that are chemically modified to distinguish them from naturally occurring parent saponins. The modified saponins have increased adjunctive activity compared to the unmodified parent saponins. Defined structures allow for comparisons of the modifying groups with respect to their respective adjunct activity and permit characterized vaccine formulations that have one or more defined saponins.

  提供了在Quillaja saponaria (QS) Molina树皮中发现的皂苷的变种，这些皂苷经过化学修饰，以使它们与自然存在的原始皂苷有所区别。经过修改的皂苷与未经修改的原始皂苷相比具有增强的辅助活性。定义的结构允许对修饰基团进行比较，以确定它们各自的辅助活性，并允许确定具有一个或多个定义的皂苷的疫苗配方。