rac-1-vinylcyclopent-2-enol | 123130-43-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: rac-1-vinylcyclopent-2-enol
• 英文别名: 1-Ethenylcyclopent-2-en-1-ol
• CAS: 123130-43-8
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: SXEUKRHGTHBHOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  rac-1-vinylcyclopent-2-enol 在 dicobalt octacarbonyl 、 potassium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 28.83h， 生成 7',7a'-dihydro-1'H-spiro[cyclopent[2]ene-1,3'-[cyclopenta[c]pyran]]-6'(4'H)-one
  参考文献：
  名称：

  生物催化光学活性叔醇

  摘要：

  摘要 最初，化学酶法制备光学活性芳香环稠环叔醇 (S)-(–)-1-methyl-1,2,3,4-tetrahydronaphthalen-1-ol-(–)-1b, (S) -(+)-1-methyl-2,3-dihydro-1H-inden-1-ol-(+)-1a 已有报道。[9] CAL-A（来自南极念珠菌的脂肪酶-A）被发现是 1b 的最佳生物催化剂，CAL-A 交联酶聚集体 (CLEA) 是 1a 的 ee 值为 20% 和 45%，酯 2b 和 2a 的 ee 值为 99和 71%。然后，环戊二烯锚定的叔烯丙基 1a'、高烯丙基 1b' 和高炔丙基 1c 醇以高 ee（高达 90%）进行酶促拆分，化学收率分别为 44%、40% 和 43%，环己基 2 -ene 在高 ee（高达 97%）中锚定叔烯丙基 3a、高烯丙基 3b 和高炔丙基 3c 醇，化学产率依次为 42%、45% 和

  DOI：

  10.1080/00397911.2016.1274032
• 作为产物：
  描述：

  溴乙烯 、 2-环戊烯酮 在 碘 、 magnesium 、 氯化铵 作用下， 以 乙醚 、 四氢呋喃 、 水 为溶剂， 反应 4.42h， 以87%的产率得到rac-1-vinylcyclopent-2-enol
  参考文献：
  名称：

  Chemoenzymatic route to various spirocyclic compounds based on enantiomerically enriched tertiary allylic, homoallylic, and homopropargylic alcohols

  摘要：

  A ring closing metathesis (RCM) reaction of dienes and an intramolecular Pauson-Khand (PKR) reaction of enynes derived from tertiary allyl, homoallyl, and homopropargyl alcohol backbones to afford the corresponding spirocyclic dihydrofuran and dihydropyrans and spirocyclic cyclopentenone pyrans, respectively, are described. Cyclopent-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols la-c have been efficiently resolved via enzymatic resolution with high ee (up to 90%) with 44%, 40%, and 43% chemical yields, respectively. Moreover, the cyclohex-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols 3a-c have also been resolved in the same manner with high ee (up to 97%) and in 42%, 45%, and 49% chemical yields. Enantiomerically enriched dienes derived from tertiary homoallyl alcohols yield the corresponding enantiomerically enriched spirocyclic dihydropyran derivatives via RCM with 74% and 78% chemical yields and with 90% and 97% ee, respectively. Moreover, enantiomerically enriched enynes derived from tertiary homoallyl alcohols afford the corresponding enantiomerically enriched cyclopentenone pyrans with spirocyclic motifs via PKR with 80% and 81% chemical yields, respectively, and as single diastereomers. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.03.004

文献信息

• Lewis acid-catalyzed oxidative rearrangement of tertiary allylic alcohols mediated by TEMPO
  作者：Jean-Michel Vatèle

  DOI：10.1016/j.tet.2009.11.104

  日期：2010.1

  Two methods for the oxidative rearrangement of tertiary allylic alcohols have been developed. Most of tertiary allylic alcohols studied were oxidized to their corresponding transposed carbonyl derivatives in excellent to fair yields by reaction with TEMPO in combination with PhIO and Bi(OTf)3 or copper (II) chloride in the presence or not of oxygen. Other primary oxidants of TEMPO such as PhI(OAc)2

  已经开发了两种方法用于叔烯丙基醇的氧化重排。通过与TEMPO结合PhIO和Bi（OTf）3或氯化铜（II）在氧气存在或不存在的情况下反应，可以将所研究的大多数叔烯丙醇氧化成其相应的转座羰基衍生物，收率极好至合理。TEMPO的诸如岛（OAC）等初级氧化剂2，中号CPBA，过硫酸氢钾®不能令人满意给予烯酮在适度低的产率。
• Copper-Catalyzed Aerobic Oxidative Rearrangement of Tertiary Allylic Alcohols Mediated by TEMPO
  作者：Jean-Michel Vatèle

  DOI：10.1055/s-0029-1217545

  日期：2009.8

  A mild method for the oxidative rearrangement of tertiary allylic alcohols to β-substituted enones using a TEMPO/CuCl 2 system, in the presence of molecular sieves, is described. Depending on the substrate, CuCl 2 was used in either a catalytic amount under an oxygen atmosphere or stoichiometrically.

  描述了在分子筛存在下使用 TEMPO/CuCl 2 系统将叔烯丙醇氧化重排为 β-取代烯酮的温和方法。取决于基材，CuCl 2 在氧气氛下以催化量或化学计量使用。
• Lewis Acid promoted Oxidative Rearrangement of Tertiary Allylic Alcohols with the PhIO/TEMPO System
  作者：Jean-Michel Vatèle

  DOI：10.1055/s-2008-1078500

  日期：——

  catalyzed oxidative rearrangement of tertiary allylic alcohols to β-disubstituted enones by the TEMPO/PhIO system is described. Bismuth triflate was found to be the most efficient catalyst for the majority of the substrates tested except for tertiary vinyl carbinols which could be transformed to enals in fair yields only when Re 2 O 7 was used as catalyst. A plausible mechanism for this oxidative rearrangement

  描述了一种温和且环境友好的方法，用于路易斯酸催化叔烯丙醇氧化重排为 TEMPO/PhIO 系统的 β-二取代烯酮。发现三氟甲磺酸铋是大多数测试底物的最有效催化剂，但叔乙烯基甲醇除外，只有当使用 Re 2 O 7 作为催化剂时，叔乙烯基甲醇才能以合理的产率转化为烯醛。讨论了这种氧化重排的合理机制。
• 1,3-Oxidative Rearrangements of Dienols
  作者：George Majetich、Stephen Condon、Kenneth Hull、Saeed Ahmad

  DOI：10.1016/s0040-4039(01)80351-8

  日期：1989.1

  Oxidation of 1-vinyl-2-cycloalken-1-ols with PDC regiospecifically affords conjugated dienones in moderate to good yields.

  用PDC区域特异性氧化1-乙烯基-2-环烯-1-醇可提供中等至良好收率的共轭二烯酮。
• MAJETICH, GEORGE;CONDON, STEPHEN;HULL, KENNETH;AHMAD, SAEED, TETRAHEDRON LETT., 30,(1989) N, C. 1033-1036
  作者：MAJETICH, GEORGE、CONDON, STEPHEN、HULL, KENNETH、AHMAD, SAEED

  DOI：——

  日期：——