[2-(2)H]-3,4,6-tri-O-benzyl-D-lyxo-hexapyranose | 1365092-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [2-(2)H]-3,4,6-tri-O-benzyl-D-lyxo-hexapyranose
• 英文别名: 3,4,6-tri-O-benzyl-2-d-D-galactal；(2R,3R,4R)-5-deuterio-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran
• CAS: 1365092-28-9
• 化学式: C₂₇H₂₈O₄
• 分子量: 417.509
• InChiKey: MXYLLYBWXIUMIT-JJAXNPIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲醇 、 [2-(2)H]-3,4,6-tri-O-benzyl-D-lyxo-hexapyranose 在 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 溴乙腈 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Iterative Synthesis of 2‐Deoxyoligosaccharides Enabled by Stereoselective Visible‐Light‐Promoted Glycosylation

  摘要：

  AbstractThe photoinitiated intramolecular hydroetherification of alkenols has been used to form C−O bonds, but the intermolecular hydroetherification of alkenes with alcohols remains an unsolved challenge. We herein report the visible‐light‐promoted 2‐deoxyglycosylation of alcohols with glycals. The glycosylation reaction was completed within 2 min in a high quantum yield (ϕ=28.6). This method was suitable for a wide array of substrates and displayed good reaction yields and excellent stereoselectivity. The value of this protocol was further demonstrated by the iterative synthesis of 2‐deoxyglycans with α‐2‐deoxyglycosidic linkages up to a 20‐mer in length and digoxin with β‐2‐deoxyglycosidic linkages. Mechanistic studies indicated that this reaction involved a glycosyl radical cation intermediate and a photoinitiated chain process.

  DOI：

  10.1002/anie.202114726
• 作为产物：
  描述：

  [2-(2)H]-3,4,6-tri-O-acetyl-D-lyxo-hexapyranose 在 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 3.0h， 生成 [2-(2)H]-3,4,6-tri-O-benzyl-D-lyxo-hexapyranose
  参考文献：
  名称：

  α-Selective Organocatalytic Synthesis of 2-Deoxygalactosides

  摘要：

  Alpha rules: A thiourea acts as an efficient organocatalyst for the glycosylation of protected galactals to form oligosaccharides containing a 2-deoxymonosaccharide moiety. The reaction is highly stereoselective for α-linkages and proceeds by way of a syn-addition mechanism.

  DOI：

  10.1002/anie.201204505

文献信息

• Gold(I)-Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals
  作者：Carlos Palo-Nieto、Abhijit Sau、M. Carmen Galan

  DOI：10.1021/jacs.7b08898

  日期：2017.10.11

  AgOTf enables the unprecedented direct and α-stereoselective catalytic synthesis of deoxyglycosides from glycals. Mechanistic investigations suggest that the reaction proceeds via Au(I)-catalyzed hydrofunctionalization of the enol ether glycoside. The room temperature reaction is high yielding and amenable to a wide range of glycal donors and OH nucleophiles.

  Au（I）与AgOTf结合使用可实现前所未有的直接和直接的α-立体选择性催化合成葡萄糖脱氧糖苷的作用。机理研究表明，该反应通过Au（I）催化的烯醇醚糖苷的加氢官能​​化而进行。室温反应是高产率的，并且适用于广泛的糖基供体和OH亲核试剂。
• Cooperative Brønsted Acid-Type Organocatalysis for the Stereoselective Synthesis of Deoxyglycosides
  作者：Carlos Palo-Nieto、Abhijit Sau、Ryan Williams、M. Carmen Galan

  DOI：10.1021/acs.joc.6b02498

  日期：2017.1.6

  α-stereoselective synthesis of deoxyglycosides using cooperative Brønsted acid-type organocatalysis has been developed. The method is tolerant of a wide range of glycoside donors and acceptors, and its versatility is exemplified in the one-pot synthesis of a trisaccharide. Mechanistic studies suggest that thiourea-induced acid amplification of the chiral acid via H-bonding is key for the enhancement

  已经开发了一种使用布朗斯台德酸型有机催化协同催化α-立体选择性合成脱氧糖苷的实用方法。该方法耐受多种糖苷供体和受体，并且其多功能性在三糖的一锅法合成中得到了例证。机理研究表明，硫脲通过氢键引起的手性酸的酸扩增是提高反应速率和产率的关键，而立体控制则取决于酸的手性。
• Stereoselective Electro‐2‐deoxyglycosylation from Glycals
  作者：Miao Liu、Kai‐Meng Liu、De‐Cai Xiong、Hanyu Zhang、Tian Li、Bohan Li、Xianjin Qin、Jinhe Bai、Xin‐Shan Ye

  DOI：10.1002/anie.202006115

  日期：2020.8.24

  report a novel and highly stereoselective electro‐2‐deoxyglycosylation from glycals. This method features excellent stereoselectivity, scope, and functional‐group tolerance. This process can also be applied to the modification of a wide range of natural products and drugs. Furthermore, a scalable synthesis of glycosylated podophyllotoxin and a one‐pot trisaccharide synthesis through iterative electroglycosylations

  我们报道了一种来自糖基的新型且高度立体选择性的电-2-脱氧糖基化反应。该方法具有出色的立体选择性，范围和功能组公差。该方法也可以用于多种天然产物和药物的改性。此外，还实现了糖基鬼臼毒素的可扩展合成和通过迭代电糖基化的单锅三糖合成。
• Substrate-Controlled Direct α-Stereoselective Synthesis of Deoxyglycosides from Glycals Using B(C₆F₅)₃ as Catalyst
  作者：Abhijit Sau、Carlos Palo-Nieto、M. Carmen Galan

  DOI：10.1021/acs.joc.8b02613

  日期：2019.3.1

  α-stereoselective synthesis of deoxyglycosides from glycals. 2,3-Unsaturated α- O-glycoside products are obtained with deactivated glycals at 75 °C in the presence of the catalyst, while 2-deoxyglycosides are formed using activated glycals that bear no leaving group at C-3 at lower temperatures. The reaction proceeds in good to excellent yields via concomitant borane activation of glycal donor and nucleophile

  B（C6F5）3使无金属的空前的基质控制的从糖类中脱氧糖苷的直接α-立体选择性合成成为可能。在催化剂存在下，在75°C下用失活的糖类获得2,3-不饱和α-O-糖苷产物，而使用在较低温度下C-3上不带有离去基团的活化的糖类形成2-脱氧糖苷。通过硼供体的糖基供体和亲核体受体的活化，该反应以良好的收率很好地进行。该方法以一系列稀有和生物学上相关的糖苷类似物的合成为例。
• Palladium‐Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals
  作者：Abhijit Sau、Ryan Williams、Carlos Palo‐Nieto、Antonio Franconetti、Sandra Medina、M. Carmen Galan

  DOI：10.1002/anie.201612071

  日期：2017.3.20

  in combination with a monodentate phosphine ligand enables the unprecedented direct and α‐stereoselective catalytic synthesis of deoxyglycosides from glycals. Initial mechanistic studies suggest that in the presence of N‐phenyl‐2‐(di‐tert‐butylphosphino)pyrrole as the ligand, the reaction proceeds via an alkoxy palladium intermediate that increases the proton acidity and oxygen nucleophilicity of the

  钯(II)与单齿膦配体相结合，能够以前所未有的方式直接和α-立体选择性催化从糖醛合成脱氧糖苷。初步机理研究表明，在N-苯基-2-(二叔丁基膦基)吡咯作为配体存在的情况下，反应通过烷氧基钯中间体进行，该中间体增加了醇的质子酸性和氧亲核性。该方法通过广泛的糖供体和受体进行了验证，包括带有烯烃官能团的底物。