benzyl α-D-glycero-pent-2-enopyranoside | 176504-85-1

• 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 α-D-glycero-pent-2-enopyranoside
• 英文别名: benzyl α-D-2,3-dideoxypent-2-enoglyceropyranoside；(3S,6S)-6-phenylmethoxy-3,6-dihydro-2H-pyran-3-ol
• CAS: 176504-85-1
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: RTCUYMOZAGDJBR-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  benzyl α-D-glycero-pent-2-enopyranoside 在 吡啶 、 四(三苯基膦)钯 、 sodium hydride 、 二甲基亚砜 、 对甲苯磺酰氯 、 三苯基膦 作用下， 反应 30.33h， 生成 benzyl 2,3,4-trideoxyribopyranosido<4,3,2-cd>-10,10-bis(methoxycarbonyl)bicyclo<3.3.0>octan-7-en-6-one
  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-dideoxy-4-O-acetyl-α-D-glycero-pent-2-enopyranoside 在 三乙胺 作用下， 以 甲醇 、 水 为溶剂， 反应 4.0h， 以1.24 g的产率得到benzyl α-D-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

文献信息

• 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.