1,5-anhydro-3-O-benzyl-4-O-(tert-butyldimethylsilyl)-2,6-dideoxy-D-ribo-hex-1-enitol

• 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: 1,5-anhydro-3-O-benzyl-4-O-(tert-butyldimethylsilyl)-2,6-dideoxy-D-ribo-hex-1-enitol
• 英文别名: 3-O-benzyl-4-O-tert-butyldimethylsilyl-6-deoxy-D-allal；tert-butyl-dimethyl-[[(2R,3R,4S)-2-methyl-4-phenylmethoxy-3,4-dihydro-2H-pyran-3-yl]oxy]silane
• 化学式: C₁₉H₃₀O₃Si
• 分子量: 334.531
• InChiKey: LQQBNURVVOMSPF-BPQIPLTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.89
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-3-O-benzyl-4-O-(tert-butyldimethylsilyl)-2,6-dideoxy-D-ribo-hex-1-enitol 在 咪唑 、 LiDBB 、 [ReOCl3(OPPh3)(SMe2)] 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 172.25h， 生成 3,4-Di-O-tert-butyldimethylsilyl-2,6-dideoxy-β-D-ribo-hexapyranosyl-(1→4)-3-O-tert-butyldimethylsilyl-2,6-dideoxy-β-D-ribohexapyranosyl-(1→4)-1,5-anhydro-3-O-tert-butyldimethylsilyl-2,6-dideoxy-D-ribo-hex-1-enitol
  参考文献：
  名称：

  Catalytic Stereoselective Synthesis of β-Digitoxosides: Direct Synthesis of Digitoxin and C1′-epi-Digitoxin

  摘要：

  A mild and atom-economic rhenium(V)-catalyzed stereoselective synthesis of beta-D-digitoxosides from 6-deoxy-D-allals has been described. This beta-selective glycosylation was achieved probably because of the formation of corresponding alpha-digitoxosides disfavored by 1,3-diaxial interaction. In addition, this method has been successfully applied to the synthesis of digitoxin trisaccharide glycal for the direct synthesis of digitwdn and C1'-epi-digitoxin.

  DOI：

  10.1021/jo4021419
• 作为产物：
  描述：

  1,2,4,6-tetra-O-acetyl-3-O-benzylallopyranose 在 吡啶 、 咪唑 、 sodium dihydrogenphosphate 、 lithium aluminium tetrahydride 、 氨 、 氢溴酸 、 乙酸酐 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 12.75h， 生成 1,5-anhydro-3-O-benzyl-4-O-(tert-butyldimethylsilyl)-2,6-dideoxy-D-ribo-hex-1-enitol
  参考文献：
  名称：

  S-连接的2-脱氧糖苷的立体选择性合成中的Umpolung反应性

  摘要：

  控制住！立体化学定义的2-脱氧糖基锂物种与不对称糖衍生的二硫键受体的前所未有的亚磺酰化作用，使得立体选择性合成α-和β-S-连接的2-脱氧寡糖成为可能。在−78°C下2-脱氧糖基苯基硫化物的还原锂化作用主要提供了轴向糖基锂物质，该物质在升温时异构化为主要为赤道的锂物质（请参见方案）。

  DOI：

  10.1002/anie.201301682

文献信息

• Iterative Synthesis of 2‐Deoxyoligosaccharides Enabled by Stereoselective Visible‐Light‐Promoted Glycosylation
  作者：Kai‐Meng Liu、Peng‐Yu Wang、Zhen‐Yan Guo、De‐Cai Xiong、Xian‐Jin Qin、Miao Liu、Meng Liu、Wan‐Ying Xue、Xin‐Shan Ye

  DOI：10.1002/anie.202114726

  日期：2022.5.9

  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.
• Synthesis of 2-Iodoglycals, Glycals, and 1,1‘-Disaccharides from 2-Deoxy-2-iodopyranoses under Dehydrative Glycosylation Conditions
  作者：Miguel Angel Rodríguez、Omar Boutureira、M. Isabel Matheu、Yolanda Díaz、Sergio Castillón、Peter H. Seeberger

  DOI：10.1021/jo701738m

  日期：2007.11.1

  [GRAPHICS]Treatment of 2-deoxy-2-iodopyranoses under dehydrative glycosylation conditions afforded pyranose glycals, 2-iodoglycals, and 1,1'-disaccharides instead of the expected glycoside products. While the product distribution revealed that this reaction is very sensitive to the configuration of the 2-deoxy-2-iodopyranose, 2-iodopyranoid glycals can be obtained almost exclusively in good yields by employing 3,4-O-isopropylidene as a cyclic bifunCtional protecting group. The behavior of 2-deoxy-2-iodopyranoses during the dehydrative elimination reaction has been analyzed in detail.
• Umpolung Reactivity in the Stereoselective Synthesis of S-Linked 2-Deoxyglycosides
  作者：Kedar N. Baryal、Danyang Zhu、Xiaohua Li、Jianglong Zhu

  DOI：10.1002/anie.201301682

  日期：2013.7.29

  Take control! An unprecedented sulfenylation of stereochemically defined 2‐deoxyglycosyl lithium species with asymmetric sugar‐derived disulfide acceptors enabled the stereoselective synthesis of both α‐ and β‐S‐linked 2‐deoxyoligosaccharides. Reductive lithiation of 2‐deoxyglycosyl phenylsulfides at −78 °C provides predominantly axial glycosyl lithium species, which upon warming isomerize to predominantly

  控制住！立体化学定义的2-脱氧糖基锂物种与不对称糖衍生的二硫键受体的前所未有的亚磺酰化作用，使得立体选择性合成α-和β-S-连接的2-脱氧寡糖成为可能。在−78°C下2-脱氧糖基苯基硫化物的还原锂化作用主要提供了轴向糖基锂物质，该物质在升温时异构化为主要为赤道的锂物质（请参见方案）。
• Catalytic Stereoselective Synthesis of β-Digitoxosides: Direct Synthesis of Digitoxin and C1′-epi-Digitoxin
  作者：Kedar N. Baryal、Surya Adhikari、Jianglong Zhu

  DOI：10.1021/jo4021419

  日期：2013.12.20

  A mild and atom-economic rhenium(V)-catalyzed stereoselective synthesis of beta-D-digitoxosides from 6-deoxy-D-allals has been described. This beta-selective glycosylation was achieved probably because of the formation of corresponding alpha-digitoxosides disfavored by 1,3-diaxial interaction. In addition, this method has been successfully applied to the synthesis of digitoxin trisaccharide glycal for the direct synthesis of digitwdn and C1'-epi-digitoxin.