3,4,6-tri-O-benzyl-α-D-glucopyranose 1,2-(pent-4-enyl orthobenzoate) | 479623-60-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-benzyl-α-D-glucopyranose 1,2-(pent-4-enyl orthobenzoate)
• 英文别名: (3aR,5R,6R,7S,7aR)-2-pent-4-enoxy-2-phenyl-6,7-bis(phenylmethoxy)-5-(phenylmethoxymethyl)-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran
• CAS: 479623-60-4
• 化学式: C₃₉H₄₂O₇
• 分子量: 622.758
• InChiKey: KYOFAUBNXNYOON-BENFPJCOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  46
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-α-D-glucopyranose 1,2-(pent-4-enyl orthobenzoate) 在 N-溴代丁二酰亚胺(NBS) 、 叔丁基二甲硅基三氟甲磺酸酯 、 水 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.03h， 生成 2-O-benzoyl-3,4,6-tri-O-benzyl-D-glucopyranose
  参考文献：
  名称：

  比较正戊烯基原酸酯和正戊烯基糖苷作为替代的糖基供体

  摘要：

  众所周知，环状1，2-糖基原酸酯经历了容易的酸催化重排成2- O-酰基糖苷，其中烷氧基以高度立体可控的过程从原酸酯转移到异头中心。相关的正戊烯基衍生物的独特之处在于原酸酯（NPOE）或它的重排产物（NPG AC）都可以作为糖基供体，并且从机械方面的考虑来看，两者都应该（或可能！）产生相同的产物。 ）是由反式原酸酯化，糖苷化，糖基酯化等产生的。实验表明，通过精心选择供体，NPOE或相关的NPG AC，可以优化从给定反应获得的产物，并特别注意反应条件，亲电子启动子，糖基受体的“大小”和实验方案。

  DOI：

  10.1016/s0040-4020(02)00671-3
• 作为产物：
  描述：

  (3aR,5R,6R,7S,7aR)-5-((benzoyloxy)methyl)-2-(pent-4-en-1-yloxy)-2-phenyltetrahydro-5H-[1,3]dioxolo[4,5-b]pyran-6,7-diyl dibenzoate 在 sodium methylate 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.67h， 生成 3,4,6-tri-O-benzyl-α-D-glucopyranose 1,2-(pent-4-enyl orthobenzoate)
  参考文献：
  名称：

  五甲甲氧基环戊二烯 (PCCP) 有机布朗斯台德酸催化 d-葡萄糖和 d-半乳糖的 N-戊烯基原酸酯 (NPOE) 与 N-碘代琥珀酰亚胺的立体选择性糖苷化

  摘要：

  在此，我们报告了在 N-碘代琥珀酰亚胺 (NIS) 存在下，利用有机布朗斯台德酸五甲氧基环戊二烯 (PCCP) 催化d -葡萄糖和d -半乳糖的正戊烯基原酸酯 (NPOE)糖苷化的初步结果。d-葡萄糖基 NPOE中的苯甲酰基和苄基保护导致 1,2-反式糖苷，而 NPOE 中的乙酰基保护导致 1,2-顺式和反式糖苷的混合物，顺式选择性 >75%，并且d-半乳糖基 NPOE 导致 1,2-原酸酯。底物范围与天然产物相关性的受体一起得到证明。本文重点介绍了利用有机布朗斯台德酸 PCCP 进行立体选择性糖苷化的前景。

  DOI：

  10.1016/j.carres.2022.108684

文献信息

• Ionic Liquid [bmim]PF₆-Mediated Synthesis of 1,2-Orthoesters of Carbohydrates and the Glycosidation Reactions of 4-Pentenyl Orthoesters
  作者：Saithalavi Anas、Valiyaveetil Sanjayan Sajisha、Rani Rajan、Rajasekaran Thirumalai Kumaran、Kokkuvayil Vasu Radhakrishnan

  DOI：10.1246/bcsj.80.553

  日期：2007.3.15

  A facile synthesis of the 1,2-orthoesters of carbohydrates in the ionic liquid [bmim]PF6 without a quaternary ammonium salt like tetrabutylammonium iodide, is described. The glycosidation reactions of 4-pentenyl orthoesters (NPOEs) with different alcohols are also discussed. The work described in this paper showed that [bmim]PF6 is an efficient and recyclable solvent for the synthesis and glycosidation reaction of orthoesters.

  描述了一种在离子液体[bmim]PF6中合成糖类1,2-邻醚的简便方法，无需使用四丁基氨铵盐如碘化四丁基铵。还讨论了4-戊烯基邻醚（NPOEs）与不同醇的糖苷化反应。本文所述的工作表明，[bmim]PF6是一种高效且可回收的溶剂，用于邻醚的合成和糖苷化反应。
• Orthoester-Based Strategy for Efficient Synthesis of the Virulent Antigenic-1,2-Linked Oligomannans of <i>Candida albicans</i>
  作者：Bert Fraser-Reid、Felix Mathew、Mateusz Mach、Kevin Hazen

  DOI：10.1055/s-2003-40350

  日期：——

  Orthobenzoates of glucose and mannose provide donor and acceptor partners to produce a disaccharide bearing a benzoyl group at the site where gluco to manno conversion is required, the inverted center being ready to function, iteratively, as the next acceptor for the gluco n-pentenyl orthobenzoate to extend the oligomannan.

  葡萄糖和甘露糖的正苯甲酸酯提供了供体和受体伙伴，可在需要将葡萄糖转化为甘露糖的部位生成带有苯甲酰基的双糖，倒置的中心可随时作为葡萄糖正戊烯基正苯甲酸酯的下一个受体，迭代地扩展低聚甘露聚糖。
• A study of n-pentenylorthoesters having manno, gluco and galacto configurations in regioselective glycosylations
  作者：K.N. Jayaprakash、Bert Fraser-Reid

  DOI：10.1016/j.carres.2006.09.022

  日期：2007.2

  Kochetkov's extensive investigations of glycosyl orthoester and their analogs as glycosyl donors revealed that the alkyl derivatives were plagued by competition between the departing alcohol and the incoming acceptor. n-Pentenyl orthoesters (NPOEs) obviate competition by sequestering the departing pentenyl alcohol as a 2-halomethyl tetrahydrofuran. Exquisitely regioselective glycosidations of diol acceptors can be carried out with NPOEs triggered specifically with Yb(OTf)(3)/NIS. However with Sc(OTf)(3), double glycosidation is the major reaction. manno, gluco and galacto NPOEs have been investigated. The latter two, which require a different experimental procedure for the manno counterpart, also give an excellent regioselectivity with Yb(OTf)(3), but the yields are much lower than with manno. (c) 2006 Elsevier Ltd. All rights reserved.
• Ytterbium(III) trifluoromethanesulfonate for specific activation of n-pentenyl orthoesters in the presence of acid-sensitive functionalities
  作者：K.N Jayaprakash、K.V Radhakrishnan、Bert Fraser-Reid

  DOI：10.1016/s0040-4039(02)01590-3

  日期：2002.9

  Various Lewis acids have been examined as agents which react with N-iodosuccinimide to release iodonium ion for activating n-pentenylorthoester (NPOE) donors, particularly for coupling to acceptors that have acid-labile protecting groups. Although many of the reagents do not tolerate cyclic acetals, (BF3Et2O)-Et-. does. However, the latter cleaves p-methoxybenzyl (PMB), making it possible to use this Lewis acid to simultaneously promote coupling of NPOEs and remove PMB groups. Of several transition metal salts investigated, ytterbium triflate is outstanding in its ability to promote NPOE Coupling With complete preservation of acid-labile protecting groups. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Comparing n-pentenyl orthoesters and n-pentenyl glycosides as alternative glycosyl donors
  作者：Mateusz Mach、Urs Schlueter、Felix Mathew、Bert Fraser-Reid、Kevin C Hazen

  DOI：10.1016/s0040-4020(02)00671-3

  日期：2002.9

  As is well known, cyclic 1,2-glycosyl orthoesters undergo ready acid catalyzed rearrangement to 2-O-acyl glycosides in which the alkoxy group is transferred from the orthoester to the anomeric center in a highly stereocontrolled process. The related n-pentenyl derivatives are unique in that either the orthoester (NPOE) or its rearrangement product (NPGAC) can function as a glycosyl donor, and mechanistic

  众所周知，环状1，2-糖基原酸酯经历了容易的酸催化重排成2- O-酰基糖苷，其中烷氧基以高度立体可控的过程从原酸酯转移到异头中心。相关的正戊烯基衍生物的独特之处在于原酸酯（NPOE）或它的重排产物（NPG AC）都可以作为糖基供体，并且从机械方面的考虑来看，两者都应该（或可能！）产生相同的产物。 ）是由反式原酸酯化，糖苷化，糖基酯化等产生的。实验表明，通过精心选择供体，NPOE或相关的NPG AC，可以优化从给定反应获得的产物，并特别注意反应条件，亲电子启动子，糖基受体的“大小”和实验方案。