1,5-anhydro-4-O-benzyl-2,6-dideoxy-L-lyxo-hex-1-enitol | 137035-65-5

• 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-4-O-benzyl-2,6-dideoxy-L-lyxo-hex-1-enitol
• 英文别名: 4-O-benzyl-L-fucal；L-arabino-Hex-5-enitol, 2,6-anhydro-1,5-dideoxy-3-O-(phenylmethyl)-；(2S,3S,4S)-2-methyl-3-phenylmethoxy-3,4-dihydro-2H-pyran-4-ol
• CAS: 137035-65-5
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: ZPIBWTYMFFSTBY-WCFLWFBJSA-N

物化性质

• 熔点：
  72-77 °C(lit.)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 安全说明：
  S24/25

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-4-O-benzyl-2,6-dideoxy-L-lyxo-hex-1-enitol 在 caesium carbonate 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.28h， 生成
  参考文献：
  名称：

  Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

  摘要：

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

  DOI：

  10.1002/anie.202109887
• 作为产物：
  描述：

  L-fucal 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium hexamethyldisilazane 、 三乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.41h， 生成 1,5-anhydro-4-O-benzyl-2,6-dideoxy-L-lyxo-hex-1-enitol
  参考文献：
  名称：

  Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

  摘要：

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

  DOI：

  10.1002/anie.202109887

文献信息

• Simple oxidation of 3-O-silylated glycals: application in deblocking 3-O-protected glycals
  作者：Andreas Kirschning、Ulrike Hary、Claus Plumeier、Monika Ries、Lars Rose

  DOI：10.1039/a807479h

  日期：——

  A high yielding allylic oxidation of 3-O-silylated glycals 5–10 with the reagent system PhI(OAc)2–TMSN3 is presented. The iodine(III) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-dihydro-4H-pyran-4-ones 11–15 than is [hydroxy(tosyloxy)iodo]benzene, the Koser reagent. Even disaccharide 9 containing the oxidation-labile phenylseleno group is smoothly oxidized to the corresponding enone 15. The hypervalent azido iodine reagent is complementary to the Koser reagent, because 3-O-benzylated or -acylated glycals cannot be oxidized. When the iodine(III)-mediated oxidation of 3-O-silylated or -benzylated glycals is followed by a reduction step, the formal 3-O-deblocking of glycals is achieved. In particular, the Luche reduction of enones obtained from the oxidation of lyxo-configured glycals 24 and 26 is highly selective and exclusively affords the corresponding lyxo-configured glycals 28 and 30. In some cases, these products can be transformed under Mitsunobu conditions into glycals with inverted configuration at C-3 in moderate yield.

  提出了一种高产率的3-O-硅烷化糖醇5–10的烯丙氧化反应，使用的试剂系统为PhI(OAc)2–TMSN3。在这些条件下生成的碘(III)物种相比于Koser试剂[羟基(托芳基羟基)碘]苯，更有效地生成以碳水化合物为基础的3-三烷基硅氧基-2,3-二氢-4H-吡喃-4-酮11–15。即使是含有易氧化的苯基硒基的二糖9，也能平稳地氧化成相应的烯酮15。超价的叠氮碘试剂与Koser试剂互补，因为3-O-苄基化或-酰基化的糖醇无法被氧化。当3-O-硅烷化或-苄基化的糖醇进行碘(III)介导的氧化后再进行还原步骤时，可以实现糖醇的形式性3-O-去堵功能。特别是，从lyxo构型的糖醇24和26氧化得到的烯酮进行Luche还原反应时，选择性极高，专门生成相应的lyxo构型的糖醇28和30。在某些情况下，这些产物可以在Mitsunobu条件下转化为C-3配置反转的糖醇，且产率适中。
• An approach for disaccharide chiron synthesis using a Ferrier-type rearrangement
  作者：Katarzyna Komor、Wiesław Szeja、Tadeusz Bieg、Nikodem Kuźnik、Gabriela Pastuch-Gawołek、Roman Komor

  DOI：10.1016/j.tetlet.2014.05.025

  日期：2014.7

  We report a new approach for the synthesis of new chiral synthons in which two unsaturated sugars are linked via a glycosidic bond. The di-unsaturated disaccharide can be further functionalized using effective, highly selective methods and used in convergent syntheses of relatively complex glycoconjugates. Our approach utilizes in situ generation of active glycosyl donors via Ferrier-type rearrangement

  我们报告了一种新的手性合成子合成的新方法，其中两个不饱和糖通过糖苷键连接。可以使用有效，高度选择性的方法将二不饱和二糖进一步官能化，并用于相对复杂的糖缀合物的融合合成中。我们的方法利用相转移条件下的Ferrier型重排原位生成活性糖基供体，并随后与亲核试剂反应。
• Approaches to the C-B-A trisaccharide of dihydroaclacinomycin by extending the chain from either side
  作者：Werner Klaffke、Dirk Springer、Joachim Thiem

  DOI：10.1016/0008-6215(92)84182-r

  日期：1992.9

  Selective benzylation of L-fucal (1) under phase-transfer conditions gave the 3- and 4-monoethers 2 and 3, respectively. Two routes, the "tail" or the "head" addition are presented, both leading to the target molecule 9, a mimic of the C-B-A trisaccharide component of dihydroaclacinomycin. Addition of glycals 2 and 3 respectively, to the acetylated glycal (7) of amicetose used as glycosyl donor gave the disaccharide glycals 6 and 8. Alternatively, glucosylation of the 4-acetate (4) of 2 with the benzyl hex-2-enopyranoside derivative 10 gave the disaccharide derivative 11. In the first case, the final glycosylation step involves the addition of 10 to disaccharide glycal 8. In the second procedure, the disaccharide alcohol 12 is obtained by O-deacetylation of 11, and serves as the glycosyl acceptor for glycal derivative 7 to give the C-B-a precursor trisaccharide derivative.
• Komor, Katarzyna; Szeja, Wieslaw; Komor, Roman, Acta poloniae pharmaceutica, 2014, vol. 71, # 6, p. 1083 - 1089
  作者：Komor, Katarzyna、Szeja, Wieslaw、Komor, Roman、Pastuchgawolek, Gabriela、Thiem, Joachim

  DOI：——

  日期：——
• Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks
  作者：Subbarao Yalamanchili、Tu‐Anh Nguyen、Alexander Zsikla、Gavin Stamper、Ashley E. DeYong、John Florek、Olivea Vasquez、Nicola L. B. Pohl、Clay S. Bennett

  DOI：10.1002/anie.202109887

  日期：2021.10.18

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.