Octyl β-D-glucopyranoside 6-O-acetate | 149263-89-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Octyl β-D-glucopyranoside 6-O-acetate
• 英文别名: octyl 6-O-acetyl-β-D-glucopyranoside；[(2R,3S,4S,5R,6R)-3,4,5-trihydroxy-6-octoxyoxan-2-yl]methyl acetate
• CAS: 149263-89-8
• 化学式: C₁₆H₃₀O₇
• 分子量: 334.41
• InChiKey: JBAHDWFMGCOBEZ-IBEHDNSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  苯甲酸酐 、 Octyl β-D-glucopyranoside 6-O-acetate 在 2,4,6-三甲基吡啶 、 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 72.0h， 生成 [(2R,3R,4S,5R,6R)-2-(acetyloxymethyl)-3,5-dihydroxy-6-octoxyoxan-4-yl] benzoate 、
  参考文献：
  名称：

  Regioselective acylation of 6-O-protected octyl β-d-glucopyranosides by DMAP catalysis

  摘要：

  Regioselectivity of acylation of 6-O-protected octyl P-D-glucopyranosides was investigated. Treatment of octyl 6-O-methyl-beta-D-glucopyranoside with isobutyric anhydride in the presence of DMAP in toluene at -40 degrees C gave 3-0-isobutyryl derivative in >99% regioselectivity. Similar treatment of octyl 6-O-TBS-beta-D-glucopyranoside at -20 degrees C also gave 3-0-isobutyryl derivative in >99% regioselectivity. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.05.098
• 作为产物：
  描述：

  乙酰氯 、 n-辛基-β-D-吡喃葡萄糖苷 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以31%的产率得到Octyl β-D-glucopyranoside 6-O-acetate
  参考文献：
  名称：

  Molecular Recognition of Carbohydrates by Zinc Porphyrins:  Lewis Acid/Lewis Base Combinations as a Dominant Factor for Their Selectivity

  摘要：

  A systematic study of the binding of carbohydrates by functionalized zinc porphyrins indicated that [5 15-bis(8-quinolyl)porphyrinato] zinc(II) (1) showed marked affinity for octyl glucoside and mannoside in CHCl3 (-Delta G degrees = 4.5-6.3 kcal-mol(-1)). Analysis of the complexation-induced shifts of the carbohydrate OH protons in the H-1 NMR revealed that receptor 1 bound the 4-OH group of mannoside and glucoside by coordination to the zinc and the 6-OH and 3-OH groups by hydrogen bonding to the quinolyl nitrogen atoms. These NMR results and comparison of binding affinity with reference receptors and ligands indicated that receptor 1 recognized the trans,trans-1,2-dihydroxy-3-(hydroxymethyl) moiety of carbohydrates by the combination of Lewis acid (zinc) and Lewis bases (quinolyl nitrogens). Poor affinities of 1 to octyl galactosides and octyl 2-O-methyl-alpha-mannoside were ascribed to neighboring group effects, where a neighboring group in ligands not directly involved in the receptor-ligand interactions had considerable influence on the affinity through destabilizing the hydrogen-bonding-network(s) in the receptor-ligand complex. The circular dichroism induced in the porphyrin Soret band by complexation with the carbohydrates displayed characteristic patterns, which parallel the patterns of the complexation-induced shifts in the H-1 NMR. The CD patterns sensitively reflected the receptor-ligand interaction modes, particularly Ligand orientation and fluctuation in the complex. variable-temperature CD revealed that glucoside was fluctuating on 1 while mannoside was rigidly fixed on 1 at room temperature. Addition of alcohols to CHCl3 suppressed the binding by 1, while addition of polar additives such as water, alcohols, phenols, and ethers assisted the binding by 3 and 4 (-Delta Delta G degrees = 0.2-0.4 kcal mol(-1)) in a low concentration range (0-1.5 mol %).

  DOI：

  10.1021/ja9713183

文献信息

• Functionalized DMAP catalysts for regioselective acetylation of carbohydrates
  作者：Takuya Kurahashi、Tadashi Mizutani、Jun-ichi Yoshida

  DOI：10.1016/s0040-4020(02)01098-0

  日期：2002.10

  New functionalized DMAPs having carboxylic acid functionality are developed for regioselective acylation of carbohydrates. In these catalysts, DMAP (4-(N,N-dimethylamino)pyridine) is linked with –COOH (–COOMe or –OSO3H in reference catalysts) via methylene spacers of different length at the dimethylamino moiety. Utilizing one of these catalysts, 3-[N-decyl-N-(4-pyridyl)amino]propionic acid (1), regioselectivity

  具有羧酸官能团的新的官能化的DMAP被开发用于碳水化合物的区域选择性酰化。在这些催化剂中，DMAP（4-（N，N-二甲基氨基）吡啶）通过二甲氨基部分上不同长度的亚甲基间隔基与–COOH（在参考催化剂中为–COOMe或–OSO 3 H）连接。利用这些催化剂中的一种，即3- [ N-癸基-N-（4-吡啶基）氨基]丙酸（1），在1- O-辛基β-d-吡喃葡萄糖苷的乙酰化中，对于伯6-OH基团的区域选择性为：与母体DMAP相比，催化活性从16％提高到89％，催化活性大大提高。催化剂1在CHCl 3的6位上，对1- O-辛基吡喃葡萄糖苷（分别对β-和α-端基的区域选择性分别为89％和88％区域选择性）和1- O-辛基吡喃半乳糖苷（对两种异构体都为100％区域选择性）的两个异构体进行区域选择性乙酰化。但在1- O-辛基甘露吡喃糖苷的情况下，可得到4-和6-单乙酸酯的近1：1混合物。进行对照实验以研究区域控制的机械方面。
• A peptide-based catalyst approach to regioselective functionalization of carbohydrates
  作者：Keith S. Griswold、Scott J. Miller

  DOI：10.1016/j.tet.2003.05.002

  日期：2003.11

  Two small peptide libraries (150 members and 36 members) have been subjected to screening experiments to evaluate their potential for regioselective (i.e. site-selective) acylation of carbohydrate monomers. Two substrates, one diol derived from N-acetyl glucosamine and one tetraol derived from glucose, have served as the test cases. In each case, the inherent regioselection of catalyzed acylation was

  已经对两个小的肽库（150个成员和36个成员）进行了筛选实验，以评估它们对碳水化合物单体进行区域选择性（即位点选择性）酰化的潜力。测试对象包括两种底物，一种是来自N-乙酰基氨基葡萄糖的二醇，另一种是来自葡萄糖的四醇。在每种情况下，催化酰化反应的固有区域选择被定义为由反应衍生而来的，其中N-甲基咪唑（NMI）用作催化剂。对于两种底物，发现肽都会干扰NMI所观察到的固有选择性。从库中，对与NMI的偏差最大的催化剂进行了优化研究。这项工作为研究扩大的肽库和发展结构-选择性关系奠定了基础，以获得可选择性衍生化立体化学复杂多元醇中独特位点的催化剂。
• Aromatic Helical Foldamers as Nucleophilic Catalysts for the Regioselective Acetylation of Octyl <i>β</i> ‐ <scp>d</scp> ‐Glucopyranoside
  作者：Geunmoo Song、Kyu‐Sung Jeong

  DOI：10.1002/cplu.202000685

  日期：2020.11

  Two indolocarbazole‐naphthyridine foldamers 2 and 3 that fold into helical conformations were prepared. The 4‐(N,N‐dimethylamino)pyridine (DMAP) moiety was introduced at one end of the foldamer strands to develop foldamer‐based catalysts for the site‐selective acylation of polyols. These foldamers adopt helical conformations containing internal cavities capable of binding octyl β‐d‐glucopyranoside

  准备了两个折叠成螺旋构象的吲哚并咔唑-萘啶折叠剂2和3。将4-（N，N-二甲基氨基）吡啶（DMAP）部分引入折叠链的一端，以开发用于多元醇的位点选择性酰化的基于折叠的催化剂。这些折叠剂采用螺旋构型，其中包含能够结合辛基β - d-吡喃葡萄糖苷的内腔。的缔合常数被确定为1.9（±0.1）×10 5 中号-1为2和2.1（±0.1）×10 5 中号-1为3在CH 2氯2在25°C下。在DMAP的存在下，以2或3作为催化剂，在相同的反应条件下对辛基β - d-吡喃葡萄糖苷进行乙酰化。DMAP催化的反应提供了单乙酰化物的随机分布（6-OAc：4-OAc：3-OAc：2-OAc = 33：24：41：2）。相反，折叠剂2和3导致6-OAc的主要形成。相对分布估计为6-OAc：4-OAc：3-OAc = 88：4：6：-0与2和6-OAc：4-OAc：3-OAc：2-OAc = 90：3： 6：1与3。
• Kurahashi, Takuya; Mizutani, Tadashi; Yoshida, Jun-Ichi, Journal of the Chemical Society. Perkin transactions I, 1999, # 4, p. 465 - 473
  作者：Kurahashi, Takuya、Mizutani, Tadashi、Yoshida, Jun-Ichi

  DOI：——

  日期：——
• Counterion-Directed Regioselective Acetylation of Octyl β-<scp>d</scp>-Glucopyranoside
  作者：Egmont Kattnig、Martin Albert

  DOI：10.1021/ol0364935

  日期：2004.3.1

  The DMAP-catalyzed acetylation Of octyl beta-D-glucopyranoside with a series of acetylating agents has been investigated. The nature of the counterion of the catalytic DMAP-acetyl complex dramatically influences the outcome of the reaction, indicating that the deprotonation of the transition state is controlling the reaction. Noncovalent interactions of the acetate ion with the substrate seem to direct the acetylation toward secondary hydroxyl groups.