Methyl-2-acetamido-6-O-(t-butyldimethylsilyl)-2-desoxy-β-D-glucopyranosid | 74265-21-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl-2-acetamido-6-O-(t-butyldimethylsilyl)-2-desoxy-β-D-glucopyranosid
• 英文别名: Methyl 2-acetamido-2-deoxy-6-O-t-butyldimethylsilyl-beta-D-glucopyranoside；N-[(2R,3R,4R,5S,6R)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-4,5-dihydroxy-2-methoxyoxan-3-yl]acetamide
• CAS: 74265-21-7
• 化学式: C₁₅H₃₁NO₆Si
• 分子量: 349.5
• InChiKey: ZNOGWZMWNIMCQH-DHGKCCLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  97.2
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Methyl-2-acetamido-6-O-(t-butyldimethylsilyl)-2-desoxy-β-D-glucopyranosid 在 3 A molecular sieve 、 焦磷酸硫胺素 、 偶氮二甲酸二乙酯 作用下， 以 苯 为溶剂， 以83.2%的产率得到Methyl-2-acetamido-3,4-anhydro-6-O-(t-butyldimethylsilyl)-2-desoxy-β-D-galactopyranosid
  参考文献：
  名称：

  Strukturelle Abwandlungen的一部分为甲硅烷基三聚氰胺/三苯膦/偶氮二碳酸酯-二乙基酯。3. Mitteilung [1]

  摘要：

  三苯基膦/偶氮二羧酸二乙酯对部分硅烷化碳水化合物的结构改性

  DOI：

  10.1002/hlca.19800630203
• 作为产物：
  描述：

  2-乙酰氨基-3,4,6-三-O-乙酰-2-脱氧-α-D-吡喃葡萄糖酰基氯 在 咪唑 、 Biorad AGMP(OH^-) resin 、 silver carbonate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl-2-acetamido-6-O-(t-butyldimethylsilyl)-2-desoxy-β-D-glucopyranosid
  参考文献：
  名称：

  Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of R- or S-Amino Acids Using Natural Sugars as Ligand Precursors

  摘要：

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.

  DOI：

  10.1021/jo970884d

文献信息

• 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。
• Selective asymmetric hydrogenation of dehydroamino acid derivatives
  申请人：E. I. Du Pont de Nemours and Company

  公开号：US05481006A1

  公开（公告）日：1996-01-02

  A process and catalyst composition are provided for the highly efficient enantioselective hydrogenation of dehydroamino acid derivatives. The catalyst composition comprises rhodium or iridium and a diphosphinite carbohydrate ligand, wherein the phosphorous atoms are attached to aromatic groups substituted with electron-donating substituents. Also provided is a means to selectively produce .alpha. amino acids in either the L or the D form, based upon use of a sugar in the ligand with phosphinites attached in an absolute Right-Left or Left-Right configuration, respectively.

  提供了一种高效的不对称氢化脱氨基酸衍生物的过程和催化剂组合物。催化剂组合物包括铑或铱和二膦酸酯糖配体，其中磷原子附着在芳香基团上，该芳香基团被电子给体取代。还提供了一种选择性地生产L或D形式α氨基酸的方法，基于在配体中使用带有绝对左右或右左构型的膦酸酯糖。
• Site-Selective Catalysis of Phenyl Thionoformate Transfer as a Tool for Regioselective Deoxygenation of Polyols
  作者：María Sánchez-Roselló、Angela L. A. Puchlopek、Adam J. Morgan、Scott J. Miller

  DOI：10.1021/jo702334z

  日期：2008.3.1

  [Graphics]We report the application of peptide-embedded imidazoles as catalysts for the site-selective delivery of the phenyl thionoformate unit as a prelude to deoxygenation reactions of polyols. Methodology was developed that allows for the synthesis of thiocarboryl derivatives based on a combination of additives that include N-alkylimidazoles and FeCl3 as co-catalysts. The use of this reagent combination leads to increased reaction rates and efficient yields relative to those of simple base-mediated reactions. In terms of controlling regioselectivity during the course of polyol modification, we found that histidine-containing peptides, in combination with FeCl3, could lead to modulation of the product distribution. Through screening of peptides and control of reaction conditions, products could be observed that reflected both the inherent preference of substrates and also reversal of inherent selectivity.
• Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of <i>R</i>- or <i>S</i>-Amino Acids Using Natural Sugars as Ligand Precursors
  作者：T. V. RajanBabu、Timothy A. Ayers、Gary A. Halliday、Kimberly K. You、Joseph C. Calabrese

  DOI：10.1021/jo970884d

  日期：1997.8.1

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.
• Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphin/Azodicarbonsäure-diäthylester. 3. Mitteilung [1]
  作者：Hannelore H. Brandstetter、Erich Zbiral

  DOI：10.1002/hlca.19800630203

  日期：1980.3.5

  Structural Modification on Partially Silylated Carbohydrates by Means of Triphenylphosphine/Diethyl Azodicarboxylate

  三苯基膦/偶氮二羧酸二乙酯对部分硅烷化碳水化合物的结构改性