5-溴-3-甲基戊-1,3-二烯 | 53776-92-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 中文名称: 5-溴-3-甲基戊-1,3-二烯
• 英文名称: (E)-5-bromo-3-methylpenta-1,3-diene
• 英文别名: 5-Bromo-3-methylpenta-1,3-diene；(3E)-5-bromo-3-methylpenta-1,3-diene
• CAS: 53776-92-4
• 化学式: C₆H₉Br
• 分子量: 161.041
• InChiKey: XSQWHDQLAHZROQ-GQCTYLIASA-N

物化性质

• 沸点：
  50 °C(Press: 10 Torr)
• 密度：
  1.245±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5-溴-3-甲基戊-1,3-二烯 以 四氢呋喃 为溶剂， 生成 (E)-3-isopropenyl-2,6-dimethyl-2-vinyl-octa-5,7-dienal
  参考文献：
  名称：

  Stereoselective synthesis of .alpha.-sinensal

  摘要：

  DOI：

  10.1021/ja00831a042
• 作为产物：
  描述：

  1,4-戊二烯 在 二叔丁基过氧化物 作用下， 以 苯 为溶剂， 生成 5-溴-3-甲基戊-1,3-二烯
  参考文献：
  名称：

  Studies of the formation and stability of pentadienyl and 3-substituted pentadienyl radicals

  摘要：

  Pentadienyl radicals and their 3-methyl and 3-hydroxy derivatives were generated from the corresponding 1,4-pentadienes. The rates of hydrogen abstraction were studied by laser flash photolysis, and the bisallylic C-H bond dissociation energies were determined by photoacoustic calorimetry. Pentadienyl radicals were also generated by monoenergetic electron bombardment of 3-tert-butyl-1,4-pentadiene, and the radical's enthalpy of formation was deduced from the appearance energy of the tert-butyl cation. Evaluation of all recent data leads to recommended values of DELTA-H(f)-degrees (pentadienyl) = 49.8 +/- 1.0 kcal mol-1 and DH-degrees ((CH2 = CH)2CH) = 76.6 +/- 1.0 kcal mol-1. The EPR spectra of 3-methylpentadienyl and several other radicals were also examined. The effect of substituents on the stabilization energy of pentadienyl radicals was assessed, and pentadienyl radicals were compared with other delocalized polyenyl radicals.

  DOI：

  10.1021/jo00019a012

文献信息

• Enantioselective Synthesis of cis-Fused Cyclooctanoids via Rhodium(I)-Catalyzed [4 + 2 + 2] Cycloadditions
  作者：Brendan C. Lainhart、Erik J. Alexanian

  DOI：10.1021/acs.orglett.5b00267

  日期：2015.3.6

  o]-type cycloadditions offer efficient, atom-economical routes to diverse complex carbocycles. Recently, such transformations have emerged as unique strategies for medium ring carbocycle synthesis. Despite the important developments in this area, however, highly enantioselective [m + n + o]-type processes accessing medium ring carbocycles have yet to be developed. Herein, a rhodium-catalyzed [4 + 2 + 2]

  催化多组分[ m + n + o ]型环加成化合物提供了高效，原子经济的途径，可通往各种复杂的碳环化合物。最近，这种转化已成为中环碳环合成的独特策略。尽管在该领域取得了重要进展，但是，高度对映选择性[ m + n + o进入中环碳环化合物的]型过程尚未开发。在本文中，报道了铑催化的烯丙二烯与丙二烯的[4 + 2 + 2]环加成反应，从而能够直接立体选择性地合成顺式融合的环辛烷类化合物。这些环加成成功地用于各种π组分，并证明了在[4 + 2 + 2]过程中高水平对映选择性的潜力。
• Studies towards Simalikalactone D and Quassimarin: Construction of an Advanced Pentacyclic Intermediate
  作者：Tony K. M. Shing、Xue Y. Zhu、Yeung Y. Yeung

  DOI：10.1002/chem.200305158

  日期：2003.11.21

  target molecules simalikalactone D and quassimarin, has been synthesized from (S)-(+)-carvone in 21 steps and with an overall yield of 12 %. The synthesis is efficient, stereocontrolled, enantiospecific, and chirality productive, creating eight new chiral centres in pentacycle, and should provide opportunities for rapid access to simalikalactone D analogues and other bioactive quassinoids. The reaction

  由（S）-（+）-香芹酮分21步合成了高级五环中间体，该中间体可进一步加工成目标分子simalikalactone D和quassimarin，其总收率为12％。该合成是有效的，立体控制的，对映体特异性的和手性生产性的，在五环中创建了八个新的手性中心，并且应提供机会快速获得马卡内酯D类似物和其他生物活性类胡萝卜素。反应顺序包括区域选择性的双羟甲基化，立体控制的环氧化，环氧亚甲基桥的形成，1,3-σ重排和分子内Diels-Alder反应作为关键步骤。
• Construction of Silicon-Containing Seven-Membered Rings by Catalytic [4 + 2 + 1] Cycloaddition through Rhodium Silylenoid
  作者：Ikuo Sasaki、Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/acs.orglett.0c00690

  日期：2020.4.17

  involving 1,3-diene, alkyne, and silylene to afford silicon-containing seven-membered rings was established. In the presence of a rhodium catalyst bearing bis(diphenylphosphino)methane (DPPM), nona-1,3-dien-8-yne derivatives reacted efficiently at 80–110 °C with boryl(isopropoxy)silane or boryl(diethyamino)silane, which reacts as the synthetic equivalent of silylene, to afford 1-silacyclohepta-2,5-dienes (2

  建立了铑催化的[4 + 2 + 1]环加成反应，该反应涉及1,3-二烯，炔烃和亚甲硅烷基，以提供含硅的七元环。在带有双（二苯基膦基）甲烷（DPPM）的铑催化剂的存在下，壬基1,3-三烯-8-炔衍生物在80–110°C下与硼基（异丙氧基）硅烷或硼基（二乙氨基）硅烷有效反应，其作为亚甲硅烷基的合成当量反应，得到1-silacyclohepta-2，5-二烯（2，5-二氢-1 H-西勒平）。七元非共轭二烯的区域发散性和化学和立体选择性官能化是通过Cs 2 CO 3或铱催化剂介导的硼氢化作用实现的。
• Concise, Enantioselective, and Versatile Synthesis of (−)-Englerin A Based on a Platinum-Catalyzed [4C+3C] Cycloaddition of Allenedienes
  作者：Ronald Nelson、Moisés Gulías、José L. Mascareñas、Fernando López

  DOI：10.1002/anie.201607348

  日期：2016.11.7

  A practical synthesis of (−)‐englerin A was accomplished in 17 steps and 11 % global yield from commercially available achiral precursors. The key step consists of a platinum‐catalyzed [4C+3C] allenediene cycloaddition that directly delivers the trans‐fused guaiane skeleton with complete diastereoselectivity. The high enantioselectivity (99 % ee) stems from an asymmetric ruthenium‐catalyzed transfer

  （-）-恩格尔林A的实用合成过程由市售的非手性前体完成，共分17个步骤完成，全球收率为11％。关键步骤包括铂催化的[4C + 3C]烯丙二烯环加成反应，该加成反应可直接提供具有完全非对映选择性的反式愈创木瓜骨架。高对映选择性（99％  ee）源自易于组装的二烯-炔酮的不对称钌催化的转移加氢。该合成还具有高度立体选择性的氧合作用和后期的铜酸盐烷基化作用，可制备以前难以获得的结构类似物。
• A Versatile, Diels–Alder Reaction-Based Approach to Prenyleudesmane Diterpenoids: A Concise Total Synthesis of Sinupol
  作者：Koichiro Ota、Hiroaki Miyaoka、Kazuo Kamaike

  DOI：10.1055/s-0037-1610757

  日期：2020.6

  Herein, a concise strategy designed to provide general and diversifiable access to various prenyleudesmane terpenoids is described and utilized in the asymmetric synthesis of a biologically active prenyleudesmane diterpenoid, sinupol, which is accomplished in a seven-step procedure.

  在此，描述了一种旨在提供对各种异戊二烯萜类化合物的通用和多样化访问的简明策略，并将其用于生物活性异戊二烯二萜类化合物 sinupol 的不对称合成，该方法通过七步程序完成。