benzyl 2,3-dideoxy-4-O-acetyl-α-D-glycero-pent-2-enopyranoside | 71978-99-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: benzyl 2,3-dideoxy-4-O-acetyl-α-D-glycero-pent-2-enopyranoside
• 英文别名: benzyl α-D-4-O-acetyl-2,3-dideoxypent-2-enoglyceropyranoside；(3S,6S)-6-(benzyloxy)-3,6-dihydro-2H-pyran-3-ylacetate；benzyl 4-O-acetyl-2,3-dideoxy-α-D-glycero-pent-2-enopyranoside；[(3S,6S)-6-phenylmethoxy-3,6-dihydro-2H-pyran-3-yl] acetate
• CAS: 71978-99-9
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: JRHWEPPLIFBIPW-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl 2,3-dideoxy-4-O-acetyl-α-D-glycero-pent-2-enopyranoside 在 吡啶 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 甲醇 、 水 为溶剂， 反应 7.0h， 生成 benzyl 2,3,4-trideoxy-4-chloro-β-L-glycero-pent-2-enopyranoside
  参考文献：
  名称：

  Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors

  摘要：

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.

  DOI：

  10.1021/jo951298s
• 作为产物：
  描述：

  benzyl 2,3-anhydro-4-O-acetyl-α-D-ribopyranoside 在 吡啶 、 sodium acetate 、 溶剂黄146 、 sodium iodide 、 三氯氧磷 作用下， 以15%的产率得到benzyl 2-iodo-2-deoxy-4-O-acetyl-α-D-arabinopyranoside
  参考文献：
  名称：

  Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors

  摘要：

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.

  DOI：

  10.1021/jo951298s

文献信息

• The use of ultrastable Y zeolites in the Ferrier rearrangement of acetylated and benzylated glycals
  作者：Pieter Levecque、David W. Gammon、Pierre Jacobs、Dirk De Vos、Bert Sels

  DOI：10.1039/b921051b

  日期：——

  The Ferrier rearrangement of a selection of protected glycals was successfully performed using a commercially available H-USY zeolite CBV-720 as catalyst, selected after screening a range of similar catalysts. By incorporating either alcohols, thiophenol, trimethylsilyl azide or allyltrimethylsilane in the reaction it was shown that a range of O-, S-, N- and C-glycosides could be formed. With benzylated glucal and galactal in particular, use of the CBV-720 catalyst led to significantly higher yields of the 2,3-dehydroglycosides than previously reported.

  使用商业可获得的H-USY沸石CBV-720作为催化剂，对一系列保护性甘露糖环进行Ferrier重排反应，该催化剂是在筛选了一系列类似的催化剂后选出的。通过在反应中加入醇、硫酚、三甲基甲硅烷基叠氮化物或烯丙基三甲基硅烷，证明了可以形成一系列O-、S-、N-和C-糖苷。特别是对于苄基化的葡萄糖醇和半乳糖醇，使用CBV-720催化剂可以获得比先前报道的2,3-脱氢糖苷的产量明显更高的产率。
• ¹³C NMR Analysis of 3,6-Dihydro-2<i>H</i>-pyrans: Assignment of Remote Stereochemistry Using Axial Shielding Effects
  作者：Mark J. Bartlett、Peter T. Northcote、Matthias Lein、Joanne E. Harvey

  DOI：10.1021/jo500678k

  日期：2014.6.20

  The rational analysis of 13C NMR axial shielding effects has enabled the assignment of remote relative stereochemistry in 3,6-oxygen-substituted 3,6-dihydro-2H-pyrans. Comparison of the 13C NMR shifts of equivalent centers in cis- and trans-substituted 3,6-dihydro-2H-pyrans allows the relative configuration at the C3 and C6 positions to be defined in diastereoisomeric mixtures. Density functional calculations

  对13 C NMR轴向屏蔽效应的合理分析已使3,6-氧-取代的3,6-二氢-2 H-吡喃具有较远的相对立体化学。比较顺式和反式取代的3,6-二氢-2 H-吡喃中等价中心的13 C NMR位移，可以在非对映异构体混合物中定义C3和C6位置的相对构型。密度泛函计算用于验证该方法并评估环系统中存在的构象偏差。最终，计算化学与这13种方法的耦合基于13 C NMR的方法为单一非对映异构体的立体化学分配提供了可靠且方便的方法。该方法为先前用于确定3，6-二氢-2 H-吡喃的相对构型的方法提供了一种简便且互补的替代方法。
• Steric constraints against [3,3]-sigmatropic rearrangement of allylic azides. A convenient approach to β-l-4-aminopent-2-enoglyceropyranosides
  作者：Cristiana Fava、Roberta Galeazzi、Giovanna Mobbili、Mario Orena

  DOI：10.1016/s0957-4166(01)00450-5

  日期：2001.10

  Starting from alkyl alpha -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 13a-c, nucleophilic substitution carried out with polymer-supported azide ion led to regioisomeric mixtures of the azides 14a-c and 15a-c. An analogous result, due to a [3,3]-sigmatropic rearrangement, was observed starting from methyl alpha -D-hex-2-enoerythropyranoside derivatives 6a and 6b. On the contrary, starting from alkyl beta -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 21a-c, azides 22a-c were exclusively obtained. and subsequently converted into the corresponding amino derivatives 23a-c. The behaviour of P-anomers 21a-c was ascribed to steric interactions in the cyclic transition state, as supported by ab initio calculations. (C) 2001 Elsevier Science Ltd. All rights reserved.