2,3,4,6-tetra-O-methyl-D-glucopyranosyl acetate | 38791-33-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-methyl-D-glucopyranosyl acetate
• 英文别名: 1-O-acetyl-2,3,4,6-tetra-O-methylglucopyranose；2,3,4,6-tetra-O-methyl-D-glucose alditol acetate；acetyl 2,3,4,6-tetra-O-methyl-α,β-D-glucopyranoside；1-O-Acetyl-tetra-O-methyl-D-glucopyranose；O¹-Acetyl-O²,O³,O⁴,O⁶-tetramethyl-ξ-D-glucopyranose；1-O-acetyl-2,3,4,6-tetra-O-methyl-α/β-D-glucopyranose；2,3,4,6-Tetra-O-methyl-D-glucopyranosylacetat；[(3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl] acetate
• CAS: 38791-33-2
• 化学式: C₁₂H₂₂O₇
• 分子量: 278.302
• InChiKey: XMEWOWGGNTUINQ-OZRWLHRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-methyl-D-glucopyranosyl acetate 在 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 生成 2,3,4,6-tetra-O-methyl-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  Rapid Preparation of Variously Protected Glycals Using Titanium(III)

  摘要：

  Glycosyl chlorides and bromides can be rapidly converted to glycals in high yield by reaction with (Cp2Ti[III]Cl)(2). This reagent tolerates a wide range of common carbohydrate protecting groups, including silyl ethers, acetals, and esters; the methodology provides a general route for the preparation of glycals substituted with both acid- and base-labile functionality. A reaction mechanism is proposed that is based on heteroatom abstraction to give an intermediate glycosyl radical. This radical reacts with a second equivalent of Ti(III) to yield a glycosyltitanium(IV) species. P-Heteroatom elimination from the glycosyltitanium(IV) complex gives the glycal.

  DOI：

  10.1021/jo982447k
• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 高氯酸 、 sodium hydride 、 碘甲烷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 90.0h， 生成 2,3,4,6-tetra-O-methyl-D-glucopyranosyl acetate
  参考文献：
  名称：

  无水醛糖甲苯磺酰腙与硼酸的偶联反应

  摘要：

  报道了 O-过乙酰化、O-过苯甲酰化、O-过甲基化和 O-过甲氧基甲基化 2,6-脱水-醛糖甲苯磺酰基腙（C-(β-d-吡喃糖基)甲醛甲苯磺酰基腙）与芳香硼酸之间的无催化剂偶联反应. 碱促进反应操作简单，底物范围广。大多数转化的主要产物是开链 1-C-芳基-hept-1-烯醇型化合物，而预期的 β-d-吡喃糖基甲基芳烃（苄基 C-糖苷）仅以次要产率形成。提供了一个机械原理来解释复杂的底物如何改变公认的反应过程。

  DOI：

  10.3390/molecules27061795

文献信息

• Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity
  作者：Chun‐Wei Chang、Chia‐Hui Wu、Mei‐Huei Lin、Pin‐Hsuan Liao、Chun‐Chi Chang、Hsiao‐Han Chuang、Su‐Ching Lin、Sarah Lam、Ved Prakash Verma、Chao‐Ping Hsu、Cheng‐Chung Wang

  DOI：10.1002/anie.201906297

  日期：2019.11.18

  Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates:

  尽管数十年来进行了大量的努力，但立体控制的化学糖基化仍然是一个主要挑战，到目前为止，仍然主要依靠反复试验。现在表明，硫糖苷的相对反应性值（RRV）是根据四种受体揭示立体选择性的指标。机理研究表明，该反应由两种不同的中间体控制：糖基三氟甲磺酸酯和来自N-卤代琥珀酰亚胺（NXS）/ TfOH的糖基卤化物。糖基卤化物的形成与α-糖苷的产生高度相关。这些发现使得能够通过使用RRV作为α/β-选择性指示剂来预见糖基化反应，并且为立体控制糖基化开发了指导方针和规则。
• Sequential Norrish Type II Photoelimination and Intramolecular Aldol Cyclization of α-Diketones: Synthesis of Polyhydroxylated Cyclopentitols by Ring Contraction of Hexopyranose Carbohydrate Derivatives
  作者：Dimitri Alvarez-Dorta、Elisa I. León、Alan R. Kennedy、Angeles Martín、Inés Pérez-Martín、Concepción Riesco-Fagundo、Ernesto Suárez

  DOI：10.1002/chem.201301230

  日期：2013.7.29

  nono‐2,3‐diulose derivatives by irradiation with visible‐light initiates a sequential Norrish type II photoelimination and aldol cyclization process that finally gives polyfunctionalized cyclopentitols. The rearrangement has been confirmed by the isolation of stable acyclic photoenol intermediates that can be independently cyclized by a thermal 5‐(enolexo)‐exo‐trig uncatalyzed aldol reaction with high diastereoselectivity

  通过可见光辐照来激发壬基2,3-二糖衍生物的最里面的羰基，引发了顺序的Norrish II型光消除和醛醇环化过程，最终形成了多官能化的环戊醇。重排已被证实由稳定的无环photoenol中间体的分离，可以通过热5-（烯醇独立地环化外型） -外型- TRIG高非对映选择性的未催化醛醇缩合反应。在最后一步中，发现1,5-氢原子转移具有较大的氘动力学同位素效应，这似乎表明醛醇缩合反应是通过协调的周环机制进行的。由于已有各种构型的吡喃糖可供使用，因此该协议已用于研究吡喃糖环取代基对醛醇环化反应的非对映选择性的影响。与其他吡喃糖环收缩方法相比，不需要过渡金属试剂，只需使用可见光和适度加热（0至60°C）即可进行顺序重排。
• Activation and synthetic applications of thiostannanes. A new method for synthesis of thio- and selenoglycosides
  作者：Tsuneo Sato、Yukihiro Fujita、Junzo Otera、Hitosi Nozaki

  DOI：10.1016/0040-4039(92)88060-i

  日期：1992.1

  Exposure of thiostannane to acetyl or methyl glycosides in the presence of a catalytic amount of Bu2Sn(OTf)2 provides thioglycosides in good yields. Selenoglycosidation is achieved in a like manner by use of selenostannane.

  在催化量的Bu 2 Sn（OTf）2的存在下将硫代锡烷暴露于乙酰基或甲基糖苷可提供高收率的硫代糖苷。通过使用硒炔诺酮以类似的方式实现硒代糖苷化。
• Synthetic studies on glycocinnamoylspermidines. Synthesis of a key intermediate of the diaminohexose moiety: Ethyl p-[4-amino-2-(tert-butoxycarbonyl)amino-2,4,6-trideoxy-α-d-glucopyranosyloxy]cinnamate
  作者：Koichi Araki、Hironobu Hashimoto、Juji Yoshimura

  DOI：10.1016/0008-6215(82)84035-4

  日期：1982.11

  Abstract A key synthetic intermediate for the diaminohexosyloxycinnamate moiety of glycocinnamoylspermidines was synthesized from d -galactose by two routes, via 3,4,6-tri-O-acetyl-2-azido-2-deoxy- d -galactopyranosyl nitrate (20) and via 1,6-anhydro-2-azido-2-deoxy-β- d -galactopyranose (12), in 16 and 22 steps, respectively.

  摘要通过3,4,6-三-O-乙酰基-2-叠氮基-2-脱氧-d-半乳糖吡喃糖基硝酸酯（20）和二苯并吡喃糖（d-galactose）的两种途径，从d-半乳糖合成了糖基肉桂酰基亚精胺的二氨基己糖氧基肉桂酸酯部分的关键合成中间体。通过1，6-脱水-2-叠氮基-2-脱氧-β-d-吡喃半乳糖（12），分别以16和22步进行。
• Preparation of 1-C-glycosyl aldehydes by reductive hydrolysis
  作者：Szabolcs Sipos、István Jablonkai

  DOI：10.1016/j.carres.2011.04.019

  日期：2011.9

  carried out using DIBAL-H to form aldimine alane intermediates which were then hydrolyzed under mildly acidic condition to provide the corresponding aldehyde derivatives. While 1-C-formyl glycal and 2-deoxy glycosyl derivatives were stable during isolation and storage 1-C-glycosyl formaldehydes in the gluco, galacto and manno series were sensitive and decomposition occurred by 2-alkyloxy elimination

  使用DIBAL-H进行各种保护的糖基氰化物的还原水解以形成醛亚胺铝烷中间体，然后将其在中等酸性条件下水解以提供相应的醛衍生物。尽管1-C-甲酰基糖基和2-脱氧糖基衍生物在分离和存储过程中是稳定的，但葡萄糖，半乳糖和甘露糖系列中的1-C-糖基甲醛很敏感，并且通过2-烷氧基消除发生了分解。开发了一种使用N，N'-二苯基乙二胺以稳定形式捕集这些醛的一锅法。糖基氰化物的还原水解以方便的方式提供了有价值的醛结构单元，可用于合成复杂的C-糖苷。