(E)-1-bromo-5-(tert-butyl-dimethylsilanyloxy)-pent-3-en-1-yne | 745788-03-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (E)-1-bromo-5-(tert-butyl-dimethylsilanyloxy)-pent-3-en-1-yne
• 英文别名: (E)-1-bromo-5-(tert-butyldimethylsilyloxy)-3-penten-1-yne；[(E)-5-bromopent-2-en-4-ynoxy]-tert-butyl-dimethylsilane
• CAS: 745788-03-8
• 化学式: C₁₁H₁₉BrOSi
• 分子量: 275.261
• InChiKey: IFWJFIRCQRGTFH-SOFGYWHQSA-N

物化性质

• 沸点：
  75 °C(Press: 0.2 Torr)
• 密度：
  1.135±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-1-bromo-5-(tert-butyl-dimethylsilanyloxy)-pent-3-en-1-yne 在 盐酸羟胺 、 氟化氢吡啶 、 乙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 3-deoxybidensyneoside C
  参考文献：
  名称：

  Total synthesis of bidensyneosides A2 and C: remarkable protecting group effects in glycosylation

  摘要：

  Bidensyneosides are a group of five recently identified polyacetylenic glucosides from Bidens parviflora WILLD, a traditional Chinese medicinal plant that contains rich bioactive natural products. It was shown that bidensyneosides inhibited both histamine release and nitric oxide production. The synthesis of bidensyneoside A2 (2) and C (4) as well as 3-deoxybidensyneoside C (5) are described. These syntheses establish a synthetic entry to the bidensyneosides and confirm the stereochemistry at C3. Furthermore, a remarkable protecting Group effect on orthoester formation was observed during the glycosylation reaction. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.08.012
• 作为产物：
  描述：

  (E)-2-penten-4-yn-1-ol 在 咪唑 、 N-溴代丁二酰亚胺(NBS) 、 silver nitrate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 4.0h， 生成 (E)-1-bromo-5-(tert-butyl-dimethylsilanyloxy)-pent-3-en-1-yne
  参考文献：
  名称：

  1-（Z）-白术醇的全合成

  摘要：

  使用新开发的碲化物合成子和使用碲化乙烯的Negishi型偶联反应的新用途，已实现了具有几种生物活性的天然聚炔醇1-（Z）-白术醇的全合成。

  DOI：

  10.1016/j.tetlet.2006.08.130

文献信息

• First Total Synthesis of Naturally Occurring (−)-Nitidon and Its Enantiomer
  作者：Fabio Bellina、Adriano Carpita、Luca Mannocci、Renzo Rossi

  DOI：10.1002/ejoc.200400101

  日期：2004.6

  The first total synthesis of naturally occurring (−)-nitidon and its enantiomer is reported. The best of the routes investigated for preparation of these enantiomerically pure compounds involves a modification of the Cadiot−Chodkiewicz reaction and the Sharpless asymmetric epoxidation of an (E)-2-ene-4,6-diyn-1-ol as key steps and proceeds in five steps and 18% overall yield. Both enantiomers of nitidon

  报道了天然存在的 (-)-nitidon 及其对映异构体的首次全合成。为制备这些对映体纯化合物而研究的最佳途径包括对 Cadiot-Chodkiewicz 反应的修饰和 (E)-2-ene-4,6-diyn-1-ol 的 Sharpless 不对称环氧化作为关键步骤和分五步进行，总产率为 18%。已发现 nitidon 的两种对映异构体和一些相关的 6-(1,3-diyn-1-yl)-2H-pyran-2-ones 在体外对人类癌细胞系表现出显着的细胞毒活性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Direct, Stereospecific Generation of (<i>Z</i>)-Disubstituted Allylic Alcohols
  作者：Sang-Jin Jeon、Ethan L. Fisher、Patrick J. Carroll、Patrick J. Walsh

  DOI：10.1021/ja061973n

  日期：2006.8.1

  A one-pot method to prepare highly functionalized (Z)-disubstituted allylic alcohols is introduced. Hydroboration of a variety of 1-bromo-1-acetylenes with dicyclohexyl borane, reaction with t-BuLi, and transmetalation to zinc generates a (Z)-disubstituted vinylzinc reagent. In situ reaction of this reagent with aldehydes generates (Z)-disubstituted allylic alcohols in high yields (81-97%). Addition

  介绍了一种制备高度官能化 (Z)-二取代烯丙醇的一锅法。各种 1-溴-1-乙炔与二环己基硼烷的硼氢化反应、与 t-BuLi 反应和金属转移生成锌，生成 (Z)-二取代的乙烯基锌试剂。该试剂与醛的原位反应以高产率 (81-97%) 生成 (Z)-二取代烯丙醇。添加到手性保护的 α- 或 β- 氧化醛以 6:1 和 18:1 之间的非对映选择性进行。在大多数情况下获得抗 Felkin 产物。
• Total synthesis of bidensyneosides A2 and C: remarkable protecting group effects in glycosylation
  作者：Benjamin W. Gung、Ryan M. Fox

  DOI：10.1016/j.tet.2004.08.012

  日期：2004.10

  Bidensyneosides are a group of five recently identified polyacetylenic glucosides from Bidens parviflora WILLD, a traditional Chinese medicinal plant that contains rich bioactive natural products. It was shown that bidensyneosides inhibited both histamine release and nitric oxide production. The synthesis of bidensyneoside A2 (2) and C (4) as well as 3-deoxybidensyneoside C (5) are described. These syntheses establish a synthetic entry to the bidensyneosides and confirm the stereochemistry at C3. Furthermore, a remarkable protecting Group effect on orthoester formation was observed during the glycosylation reaction. (C) 2004 Elsevier Ltd. All rights reserved.
• Total synthesis of 1-(Z)-atractylodinol
  作者：Juliana M. Oliveira、Gilson Zeni、Ivani Malvestiti、Paulo H. Menezes

  DOI：10.1016/j.tetlet.2006.08.130

  日期：2006.11

  The total synthesis of 1-(Z)-atractylodinol, a natural polyacetylenic alcohol with several biological activities, has been achieved using a newly developed telluride synthon and a novel use for the Negishi type coupling reaction employing vinyl tellurides.

  使用新开发的碲化物合成子和使用碲化乙烯的Negishi型偶联反应的新用途，已实现了具有几种生物活性的天然聚炔醇1-（Z）-白术醇的全合成。