(2R,3S,6S)-2-Hydroxymethyl-6-(3-methyl-but-2-enyloxy)-3,6-dihydro-2H-pyran-3-ol | 1026636-56-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (2R,3S,6S)-2-Hydroxymethyl-6-(3-methyl-but-2-enyloxy)-3,6-dihydro-2H-pyran-3-ol
• 英文别名: (2R,3S,6S)-2-(hydroxymethyl)-6-(3-methylbut-2-enoxy)-3,6-dihydro-2H-pyran-3-ol
• CAS: 1026636-56-5
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: DIVAIQKIVNDEKO-AXFHLTTASA-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：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3S,6S)-2-Hydroxymethyl-6-(3-methyl-but-2-enyloxy)-3,6-dihydro-2H-pyran-3-ol 在 咪唑 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 39.0h， 生成 [(2R,3S,6S)-3-(2-Bromo-allyloxy)-6-(3-methyl-but-2-enyloxy)-3,6-dihydro-2H-pyran-2-ylmethoxy]-tert-butyl-dimethyl-silane
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 2. Synthesis of Enantiopure Tricyclic Compounds

  摘要：

  The bromo substituted unsaturated carbohydrates 3a-f were prepared from 3,4,6-tri-O-acetyl-D-glucal by Ferrier reaction with the appropriate allylic or homoallylic alcohol, deacetylation followed by monosilylation with TBDMSCl, and then alkylation with BrCH2CBr=CH2. The N- and C-analogues 4a,b were synthesized by palladium alkylation of the intermediate carbonate with TsNHCH2CBr=CH2 and (MeO2C)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a, 4a, and 4b with a catalytic amount of Pd(OAc)(2)/PPh3 in CH3CN/H2O, in the presence of Bu4NHSO4 and NEt3, afforded the tricyclic compounds 5, 6, and 7, respectively. Under the same conditions, the analogue tricyclic compounds 8, 9, and 10 were formed starting from 3b-d. In the case of compounds 3e and 3f, the formation of the bicyclic glucal 11 via an already described beta-alkoxyelimination was only observed. Moreover, trapping of the sigma-alkylpalladium intermediate obtained from 3e with an external nucleophile yielded the 2-deoxy carbohydrate 12 and the 2,3-unsaturated sugar 13, using respectively sodium formate and sodium tetraphenylborate.

  DOI：

  10.1021/jo970817j
• 作为产物：
  描述：

  异戊烯醇 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 苯 为溶剂， 生成 (2R,3S,6S)-2-Hydroxymethyl-6-(3-methyl-but-2-enyloxy)-3,6-dihydro-2H-pyran-3-ol
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 2. Synthesis of Enantiopure Tricyclic Compounds

  摘要：

  The bromo substituted unsaturated carbohydrates 3a-f were prepared from 3,4,6-tri-O-acetyl-D-glucal by Ferrier reaction with the appropriate allylic or homoallylic alcohol, deacetylation followed by monosilylation with TBDMSCl, and then alkylation with BrCH2CBr=CH2. The N- and C-analogues 4a,b were synthesized by palladium alkylation of the intermediate carbonate with TsNHCH2CBr=CH2 and (MeO2C)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a, 4a, and 4b with a catalytic amount of Pd(OAc)(2)/PPh3 in CH3CN/H2O, in the presence of Bu4NHSO4 and NEt3, afforded the tricyclic compounds 5, 6, and 7, respectively. Under the same conditions, the analogue tricyclic compounds 8, 9, and 10 were formed starting from 3b-d. In the case of compounds 3e and 3f, the formation of the bicyclic glucal 11 via an already described beta-alkoxyelimination was only observed. Moreover, trapping of the sigma-alkylpalladium intermediate obtained from 3e with an external nucleophile yielded the 2-deoxy carbohydrate 12 and the 2,3-unsaturated sugar 13, using respectively sodium formate and sodium tetraphenylborate.

  DOI：

  10.1021/jo970817j

文献信息

• Palladium-Mediated Cyclization on Carbohydrate Templates. 2. Synthesis of Enantiopure Tricyclic Compounds
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo970817j

  日期：1997.10.1

  The bromo substituted unsaturated carbohydrates 3a-f were prepared from 3,4,6-tri-O-acetyl-D-glucal by Ferrier reaction with the appropriate allylic or homoallylic alcohol, deacetylation followed by monosilylation with TBDMSCl, and then alkylation with BrCH2CBr=CH2. The N- and C-analogues 4a,b were synthesized by palladium alkylation of the intermediate carbonate with TsNHCH2CBr=CH2 and (MeO2C)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a, 4a, and 4b with a catalytic amount of Pd(OAc)(2)/PPh3 in CH3CN/H2O, in the presence of Bu4NHSO4 and NEt3, afforded the tricyclic compounds 5, 6, and 7, respectively. Under the same conditions, the analogue tricyclic compounds 8, 9, and 10 were formed starting from 3b-d. In the case of compounds 3e and 3f, the formation of the bicyclic glucal 11 via an already described beta-alkoxyelimination was only observed. Moreover, trapping of the sigma-alkylpalladium intermediate obtained from 3e with an external nucleophile yielded the 2-deoxy carbohydrate 12 and the 2,3-unsaturated sugar 13, using respectively sodium formate and sodium tetraphenylborate.