[(2R,3S,6S)-3-(2-bromoprop-2-enoxy)-6-but-3-enoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane | 174467-62-0

• 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)-3-(2-bromoprop-2-enoxy)-6-but-3-enoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 174467-62-0
• 化学式: C₁₉H₃₃BrO₄Si
• 分子量: 433.458
• InChiKey: OHKCJUJGZXKSLZ-KSZLIROESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.18
• 重原子数：
  25
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(2R,3S,6S)-3-(2-bromoprop-2-enoxy)-6-but-3-enoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane 在 palladium diacetate 、 四丁基溴化铵 、 三乙胺 、 三苯基膦 作用下， 以 水 、 乙腈 为溶剂， 反应 3.0h， 以78%的产率得到1,2,3,4-tetradeoxy-2',3',4',5'-tetrahydro-6-O-(tert-butyldimethylsilyl)-4'-methylene-D-ribo-hex-1-enopyranoso-[4,3-b]furan
  参考文献：
  名称：

  碳水化合物模板上钯介导的环化成双环吡喃糖苷的新途径

  摘要：

  描述了一种新的有效途径，通过钯（0）催化的级联环化反应生成双环吡喃糖苷。合适的2，3-不饱和烯丙基糖苷在光滑的Jeffery条件下进行Heck反应，以高收率生产三环衍生物。

  DOI：

  10.1016/0040-4039(95)02096-9
• 作为产物：
  描述：

  but-3-en-1-yl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 咪唑 、 sodium methylate 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 39.0h， 生成 [(2R,3S,6S)-3-(2-bromoprop-2-enoxy)-6-but-3-enoxy-3,6-dihydro-2H-pyran-2-yl]methoxy-tert-butyl-dimethylsilane
  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 cyclisation on carbohydrate templates A new route to bis-annulated pyranosides
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1016/0040-4039(95)02096-9

  日期：1996.1

  A new and efficient route to bis-annulated pyranosides by palladium(0)-catalysed cascade cyclisation is described. The appropriate 2,3-unsaturated allylglycosides are subjected to Heck reaction under smooth Jeffery's conditions to produce the tricyclic derivatives in good yields.

  描述了一种新的有效途径，通过钯（0）催化的级联环化反应生成双环吡喃糖苷。合适的2，3-不饱和烯丙基糖苷在光滑的Jeffery条件下进行Heck反应，以高收率生产三环衍生物。
• 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.