2-((5-bromo-3-pentynyl)oxy)tetrahydro-2H-pyran | 68931-45-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 2-((5-bromo-3-pentynyl)oxy)tetrahydro-2H-pyran
• 英文别名: 2-(5-bromopent-3-ynyloxy)tetrahydropyran；2-(5-bromopent-3-ynoxy)oxane
• CAS: 68931-45-3
• 化学式: C₁₀H₁₅BrO₂
• 分子量: 247.132
• InChiKey: QSYMUTKVDNLGON-UHFFFAOYSA-N

物化性质

• 沸点：
  309.4±42.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((5-bromo-3-pentynyl)oxy)tetrahydro-2H-pyran 在 N-碘代丁二酰亚胺 、 camphor-10-sulfonic acid 、 silver nitrate 、 lithium diisopropyl amide 作用下， 以 甲醇 为溶剂， 生成 (3R,4R)-1-(tert-Butyl-dimethyl-silanyl)-3-(5-hydroxy-pent-2-ynyl)-4-(3-iodo-prop-2-ynyl)-azetidin-2-one
  参考文献：
  名称：

  通过立体选择性频哪醇偶联获得 β-内酰胺稠合烯二炔（“Lactenediynes”）的新方法

  摘要：

  报告了通过在双键位点闭合十元环来快速合成未官能化的乳糖二炔 3。在已知方法失败后，由于双 (alk-2-ynal) 7 的高度立体选择性、钒 (II) 介导的频哪醇偶联，最终成功实现了这种闭合。

  DOI：

  10.1002/(sici)1099-0690(200003)2000:6<939::aid-ejoc939>3.0.co;2-q
• 作为产物：
  描述：

  5-(tetrahydro-2H-pyran-2-yloxy)-2-pentyn-1-ol 在 四溴化碳 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 以59 %的产率得到2-((5-bromo-3-pentynyl)oxy)tetrahydro-2H-pyran
  参考文献：
  名称：

  炔基酯酰胺环化生成吡嗪-1(2H)-酮：在合成帕拉明和二溴邻苯二甲酸酯中的应用

  摘要：

  在此，我们报道了一种有效的1,5,7-三氮杂双环[4.4.0]dec-5-ene（TBD）催化的串联分子间酰胺化和炔基酯的区域选择性分子内6- exo -dig环化，以有效地获得pyrazine-1( 2 H )-一个支架。这种有机催化的 [5 + 1] 成环具有涉及两个成环伴侣的广泛底物范围。实现了波胺的全合成和二溴邻苯二甲酸酯天然产物的形式合成，展示了该方法的应用潜力。

  DOI：

  10.1021/acs.joc.3c02157

文献信息

• Highly Stereo- and Regioselective Hydrocarboxylation of Diynes with Carbon Dioxide
  作者：Tao Cao、Shengming Ma

  DOI：10.1021/acs.orglett.6b00028

  日期：2016.4.1

  A nickel-catalyzed three-component hydrocarboxylation of diynes with ZnEt2 and CO2 (1 atm) is disclosed. With this method, symmetric/nonsymmetric diynes could be reacted smoothly with very high stereo- and regioselectivity, affording conjugated 2,4-alkadienoic acids incorporated with five- or six-membered rings efficiently. A stepwise non-oxidative cyclometalation mechanism was proposed based on careful

  公开了用ZnEt 2和CO 2（1atm）的二炔的镍催化的三组分加氢羧化。用这种方法，对称/不对称二炔可以以非常高的立体选择性和区域选择性平滑反应，从而有效地提供了结合有五元或六元环的共轭2,4-链二烯酸。在仔细的机理研究的基础上，提出了一种逐步的非氧化性环金属化机理。
• <i>Michael</i>-Addition von Thiocarbonsäureestern Anwendung bei der Synthese von (±)-Jasminketolacton
  作者：Hans Gerlach、Peter Künzler

  DOI：10.1002/hlca.19780610721

  日期：1978.11.1

  Michael addition of carbothioates. Application to the synthesis of (±)-jasmine ketolactone

  迈克尔加硫代碳酸盐。在合成（±）-茉莉酮内酯中的应用
• A General Synthetic Approach to the (20S)-Camptothecin Family of Antitumor Agents by a Regiocontrolled Cascade Radical Cyclization of Aryl Isonitriles
  作者：Hubert Josien、Sung-Bo Ko、David Bom、Dennis P. Curran

  DOI：10.1002/(sici)1521-3765(199801)4:1<67::aid-chem67>3.0.co;2-f

  日期：1998.1

  A general and efficient synthesis of (20S)-camptothecin (1a) is reported. A key common intermediate containing the pyridone and lactone (DE) rings of camptothecin and most derivatives was constructed from 2-trimethylsilyl-6-methoxypyridine by a series of metalation reactions and a Heck cyclization to provide an achiral bicyclic enol ether. Sharpless asymmetric dihydroxylation followed by lactol oxidation and iododesilylation produced the key intermediate in 94% enantiomeric excess. Alkylation with propargyl bromide and a cascade radical reaction with phenyl isonitrile then produced 1a. About 20 other penta- and hexacyclic analogues of camptothecin with differing single or multiple substituents at C7, C9, C10, C11, and/or C12 were made by changing the propargylating agent and the isonitrile. Included among these are several drug candidates and the approved drugs topotecan and irinotecan. The synthesis of the prodrug irinotecan is direct one that does not pass through the active metabolite. The use of ortho-trimethylsilyl-substituted isonitriles allows the regioselective synthesis of camptothecin analogues in cases where isomeric mixtures are formed from the parent isonitriles. The synthesis of the derivatives relies on the broad scope and functional group tolerance of the key cascade radical reaction.
• Selective N-functionalization of 6-substituted-2-pyridones
  作者：Hui Liu、Sung-Bo Ko、Hubert Josien、Dennis P. Curran

  DOI：10.1016/0040-4039(95)01917-7

  日期：1995.12

  6-Substituted-2-pyridones can be selectively N-alkylated by treatment with NaH/LiBr in a mixture of DMF and DME. Yields of N-propargylated, N-allylated, and other N-functionalized products are good, and only small amounts of the isomeric O-alkylated product (<10%) are typically formed.
• 10.1002/1099-0690(200107)2001:13<2577::aid-ejoc2577<3.0.co;2-b
  作者：Dumez, Estelle、Faure, Robert、Dulcere, Jean-Pierre

  DOI：10.1002/1099-0690(200107)2001:13<2577::aid-ejoc2577<3.0.co;2-b

  日期：——