methyl 2,3-di-O-benzyl-α-D-galactopyranoside | 29388-46-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-di-O-benzyl-α-D-galactopyranoside
• 英文别名: (2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-methoxy-4,5-bis(phenylmethoxy)oxan-3-ol
• CAS: 29388-46-3
• 化学式: C₂₁H₂₆O₆
• 分子量: 374.434
• InChiKey: AOHYQGVMTDLXSL-IFLJBQAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  ——	methyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-α-D-galactopyranoside	354114-10-6	C32H34O6	514.618
  ——	methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-galactopyranoside	——	C28H30O6	462.543
  ——	(2R,4aR,6S,7R,8S,8aS)-6-methoxy-2-phenyl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine	7177-79-9	C28H30O6	462.543
  ——	methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-galactopyranoside	29600-81-5	C28H30O6	462.543
  ——	methyl 4,6-O-benzylidene-α-D-galactopyranoside	64552-06-3	C14H18O6	282.293
  ——	methyl 4,6-O-benzylidene-α-D-galactopyranoside	4288-93-1	C14H18O6	282.293
  甲基4,6-O-[(4-甲氧基苯基)亚甲基]-2,3-二-O-(苯基甲基)-ALPHA-D-吡喃半乳糖苷	methyl 2,3-di-O-benzyl-4,6-O-(4-methoxybenzylidene)-α-D-galactopyranoside	94902-59-7	C29H32O7	492.569
  Α-D-乳酸吡喃糖苷甲酯	methyl α-D-galactopyranoside	3396-99-4	C7H14O6	194.185

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	Methyl-2,3-di-O-benzyl-6-desoxy-α-D-galactopyranosid	13231-27-1	C21H26O5	358.434
  ——	methyl 2,3,6-tri-O-benzyl-α-D-galactopyranoside	——	C28H32O6	464.558
  ——	methyl 2,3-di-O-benzyl-β-L-altrofuranoside	16895-91-3	C21H26O6	374.434
  ——	1,6-Anhydro-2,3-di-O-benzyl-α-D-galactofuranose	118475-44-8	C20H22O5	342.392
  ——	methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-galactopyranoside	——	C28H30O6	462.543
  ——	methyl 2,3-di-O-benzyl-6-bromo-6-deoxy-α-D-galactopyranoside	129077-17-4	C21H25BrO5	437.331
  ——	methyl 4,6-di-O-butyryl-2,3-di-O-benzyl-α-D-galactopyranoside	132891-76-0	C29H38O8	514.616
  ——	methyl 2,3-di-O-benzyl-4,6-O-(2,3,4,6-tetra-O-benzyl-D-mannopyranosylidene)-α-D-galactopyranoside	313640-15-2	C55H58O11	895.059
  ——	methyl 2,3-di-O-benzyl-4,6-O-(2,3,4-tri-O-benzyl-D-fucopyranosylidene)-α-D-galactopyranoside	313640-16-3	C48H52O10	788.935
  ——	methyl 2,3-di-O-benzyl-4,6-O-(2,3,4-tri-O-benzyl-L-rhamnopyranosylidene)-α-D-galactopyranoside	313640-18-5	C48H52O10	788.935

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-benzyl-α-D-galactopyranoside 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II) 、 正丁基锂 、 二乙胺基三氟化硫 、 硫酸 、 10% Pd(OH)2/C 、 水 、 氢溴酸 、 氢气 、 碘 、 二正丁基氧化锡 、 溶剂黄146 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 66.41h， 生成 dibenzyl 2,3,6-tri-O-benzoyl-5-deoxy-5-fluoro-α-D-galactofuranose monophosphate
  参考文献：
  名称：

  Fluorosugar Chain Termination Agents as Probes of the Sequence Specificity of a Carbohydrate Polymerase

  摘要：

  Naturally occurring carbohydrate polymers are ubiquitous. They are assembled by polymerizing glycosyltransferases, which can generate polysaccharide products with repeating sequence patterns. The fidelity of enzymes of this class is unknown. We report a method for testing the fidelity of carbohydrate polymerase pattern deposition: we synthesized fluorosugar donors and used them as chain termination agents. The requisite nucleotide fluorosugars could be produced from a single intermediate using the Jacobsen catalyst in a kinetically controlled separation of diastereomers. The resulting fluorosugar donors were used by the galactofuranosyltransferase GlfT2 from Mycobacterium tuberculosis, and the data indicate that this enzyme mediates the cell wall galactan production through a sequence-specific polymerization.

  DOI：

  10.1021/ja301723p
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 水 、 sodium hydride 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 methyl 2,3-di-O-benzyl-α-D-galactopyranoside
  参考文献：
  名称：

  A green and convenient method for regioselective mono and multiple benzoylation of diols and polyols

  摘要：

  An efficient method for regioselective benzoylation of diols and polyols was developed. The benzoylation is catalyzed by only 0.2 equiv of benzoate anion in acetonitrile with the addition of a stoichiometric amount of benzoic anhydride under very mild condition, leading to high yields. Compared with all other methods, this method shows particular advantage in regioselective multiple benzoylation of polyols, and in avoiding the use of any metal-based catalysts and any amine bases, which is more environment friendly. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.12.074

文献信息

• Regioselective Benzoylation of Diols and Carbohydrates by Catalytic Amounts of Organobase
  作者：Yuchao Lu、Chenxi Hou、Jingli Ren、Xiaoting Xin、Hengfu Xu、Yuxin Pei、Hai Dong、Zhichao Pei

  DOI：10.3390/molecules21050641

  日期：——

  A novel metal-free organobase-catalyzed regioselective benzoylation of diols and carbohydrates has been developed. Treatment of diol and carbohydrate substrates with 1.1 equiv. of 1-benzoylimidazole and 0.2 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN under mild conditions resulted in highly regioselective benzoylation for the primary hydroxyl group. Importantly, compared to most commonly

  已经开发出一种新型的无金属有机碱催化的二醇和碳水化合物的区域选择性苯甲酰化。用 1.1 当量处理二醇和碳水化合物底物。1-苯甲酰咪唑和 0.2 当量。1,8-二氮杂双环[5.4.0] undec-7-ene (DBU) 在温和条件下在 MeCN 中的反应导致伯羟基的高度区域选择性苯甲酰化。重要的是，与最常用的伯羟基保护基团相比，苯甲酰基保护基团提供了一种新的保护策略。
• Oxidation of stannylene derivatives of carbohydrates using 1,3-dibromo-5,5-dimethylhydantoin
  作者：Peter Söderman、Göran Widmalm

  DOI：10.1016/s0008-6215(99)00032-4

  日期：1999.3

  Abstract 1,3-Dibromo-5,5-dimethylhydantoin (DBDMH) has been used to oxidize stannylene derivatives of monosaccharides to give hydroxy-ketones thereof. Oxidations could be performed rapidly and in good-to-excellent yields. The oxidizing reagent DBDMH thus provides a convenient alternative to existing methods.

  摘要1,3-二溴-5,5-二甲基乙内酰脲（DBDMH）已被用于氧化单糖的亚锡衍生物以产生其羟基酮。氧化可以快速进行，并具有良好至优异的产率。因此，氧化剂DBDMH为现有方法提供了一种方便的替代方法。
• Synthesis of methyl derivatives of uronic acids. I. Synthesis of methyl (methylα-D-galactopyranosid)uronate and its 2-, 3-, and 4-O-methyl ethers
  作者：V. I. Grishkovets、A. E. Zemlyakov、V. Ya. Chirva

  DOI：10.1007/bf00580445

  日期：1982.5

  Alternative unidirectional methods for synthesizing methyl (methyl α-D-galactopyranosid)uronate and its mono-O-methyl ethers by the oxidation (with CrO3-H2SO4-acetone) of the corresponding methyl O-benzyl-O-methyl-α-D-galactopyranosides having unsubstituted 6-OH groups to the corresponding methyl O-benzyl-O-methyl-α-D-galactouronic acids followed by esterification with CH2N2 and the catalytic hydrogenolysis

  通过相应的甲基 O-苄基-O-甲基-α-D-氧化（用 CrO3-H2SO4-丙酮）合成（甲基 α-D-吡喃半乳糖苷）糖醛酸甲酯及其单-O-甲基醚的替代单向方法提出了具有未取代的 6-OH 基团的吡喃半乳糖苷与相应的甲基 O-苄基-O-甲基-α-D-半乳糖醛酸，然后用 CH2N2 酯化和苄基的催化氢解。
• Regio/site-selective alkylation of substrates containing a <i>cis</i>-, 1,2- or 1,3-diol with ferric chloride and dipivaloylmethane as the catalytic system
  作者：Jian Lv、Yu Liu、Jia-Jia Zhu、Dapeng Zou、Hai Dong

  DOI：10.1039/c9gc04126e

  日期：——

  In this study, we reported the regio/site-selective alkylation of substrates containing a cis-, 1,2- or 1,3-diol with FeCl3 as a key catalyst. A catalytic system consisting of FeCl3 (0.01–0.1 equiv.) and dipivaloylmethane (FeCl3/dipivaloylmethane = 1/2) was used to catalyze the alkylation in the presence of a base. The produced selectivities and isolated yields were similar to those obtained by methods

  在这项研究中，我们报道了含有顺式-，1,2-或1,3-二醇的底物的区域/位置选择性烷基化，其中FeCl 3为关键催化剂。由FeCl 3（0.01-0.1当量）和二戊酰基甲烷（FeCl 3 / dipivaloylmethane = 1/2）组成的催化体系用于在存在碱的情况下催化烷基化。在大多数情况下，所产生的选择性和分离的产率与使用相同量的FeL 3（L =酰基丙酮配体）作为催化剂的方法所获得的相似。先前报道的用于烷基化的FeL 3催化剂不可商购，并且必须在使用前合成。相反，FeCl 3苯二甲酰甲烷（Hdipm）和二甲戊酰甲烷（Hdipm）是实验室中非常普遍且廉价的无毒试剂，因此使该方法更加绿色且易于操作。机理研究首次证实，FeCl 3最初在乙腈中存在碱的情况下与两当量的Hdipm反应形成[Fe（dipm）3 ]，然后在[[]之间形成五或六元环中间体。 Fe（dipm）3 ]和底物的两个羟
• Regioselective Sulfonylation/Acylation of Carbohydrates Catalyzed by FeCl₃ Combined with Benzoyltrifluoroacetone and Its Mechanism Study
  作者：Jian Lv、Jia-Jia Zhu、Yu Liu、Hai Dong

  DOI：10.1021/acs.joc.9b03128

  日期：2020.3.6

  A catalytic amount of FeCl3 combined with benzoyl trifluoroacetone (Hbtfa) (FeCl3/Hbtfa = 1/2) was used to catalyze sulfonylation/acylation of diols and polyols using diisopropylethylamine (DIPEA) or potassium carbonate (K2CO3) as a base. The catalytic system exhibited high catalytic activity, leading to excellent isolated yields of sulfonylation/acylation products with high regioselectivities. Mechanism

  使用二异丙基乙胺（DIPEA）或碳酸钾（K2CO3）作为碱，将催化量的FeCl3与苯甲酰基三氟丙酮（Hbtfa）（FeCl3 / Hbtfa = 1/2）结合用于催化二醇和多元醇的磺酰化/酰化。该催化体系表现出高催化活性，导致具有高区域选择性的磺酰化/酰化产物的优异分离产率。机理研究表明，FeCl3最初在碱性条件下于室温下于溶剂乙腈中以两倍的Hbtfa量形成[Fe（btfa）3]（btfa =苯甲酰基三氟丙酮酸酯）。然后，在碱的存在下，Fe（btfa）3和底物的两个羟基形成五元或六元环中间体。环状中间体和磺酰化试剂之间的随后反应导致底物的选择性磺酰化。所有关键中间体均在高分辨率质谱分析中捕获，因此首次证明了这种机理。