1-(cyclohex-1-enyl)cyclobutanol | 70624-97-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(cyclohex-1-enyl)cyclobutanol
• 英文别名: 1-(cyclohex-1-en-1-yl)cyclobutanol；1-(cyclohex-1-en-1-yl)cyclobutan-1-ol；1-Cyclohexenylcyclobutanol；1-(Cyclohexen-1-yl)cyclobutan-1-ol
• CAS: 70624-97-4
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: MKIIOKPWFXRQIV-UHFFFAOYSA-N

物化性质

• 沸点：
  243.2±19.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  1-(cyclohex-1-enyl)cyclobutanol 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.0h， 以99%的产率得到1-(7-oxabicyclo[4.1.0]hept-1-yl)cyclobutanol
  参考文献：
  名称：

  Investigations of α-Siloxy−Epoxide Ring Expansions Forming 1-Azaspirocyclic Ketones

  摘要：

  The construction of 1-azaspirocyclic cycloalkanones using a siloxy-epoxide semipinacol ring expansion process was examined. Functionalized 1-azaspiro[5.5]undecan-7-ones (1-azaspirocyclic cyclohexanones) proceeded in high chemical yields with complete diastereoselectivity using titanium tetrachloride as the Lewis acid promoter. The formation of functionalized 6-azaspiro[5.4]-decan-1-ones (1-azaspirocyclic cyclopentanones) proceeded in high chemical yield with little diastereoselectivity. Modification of reaction parameters such as the Lewis acid promoter or the nature of the silyl ether allowed for the preferential formation of either ("anti" or "syn" 1,2 alkyl shift) diastereomeric product. An explanation for the different reactivity profiles between the cyclobutanol silyl ethers and cyclopentanol silyl ethers is provided.

  DOI：

  10.1021/jo049356+
• 作为产物：
  描述：

  环丁酮 、 1-氯环己烯 在 lithium 作用下， 以 乙醚 为溶剂， 反应 14.5h， 以73%的产率得到1-(cyclohex-1-enyl)cyclobutanol
  参考文献：
  名称：

  Investigations of α-Siloxy−Epoxide Ring Expansions Forming 1-Azaspirocyclic Ketones

  摘要：

  The construction of 1-azaspirocyclic cycloalkanones using a siloxy-epoxide semipinacol ring expansion process was examined. Functionalized 1-azaspiro[5.5]undecan-7-ones (1-azaspirocyclic cyclohexanones) proceeded in high chemical yields with complete diastereoselectivity using titanium tetrachloride as the Lewis acid promoter. The formation of functionalized 6-azaspiro[5.4]-decan-1-ones (1-azaspirocyclic cyclopentanones) proceeded in high chemical yield with little diastereoselectivity. Modification of reaction parameters such as the Lewis acid promoter or the nature of the silyl ether allowed for the preferential formation of either ("anti" or "syn" 1,2 alkyl shift) diastereomeric product. An explanation for the different reactivity profiles between the cyclobutanol silyl ethers and cyclopentanol silyl ethers is provided.

  DOI：

  10.1021/jo049356+

文献信息

• Enantioselective Organocatalytic Fluorination-Induced Wagner-Meerwein Rearrangement
  作者：Fedor Romanov-Michailidis、Laure Guénée、Alexandre Alexakis

  DOI：10.1002/anie.201303527

  日期：2013.8.26

  Cracked under strain: Strained allylic cyclobutanols and cyclopropanols readily undergo a ring expansion described by the title rearrangement. This reaction is promoted by catalytic amounts of 1 and displays high tolerance with respect to the substrate scope. The corresponding β‐fluoro spiroketone products are isolated in high yields and with excellent stereoselectivities. EDG=electron‐donating group

  在应变下破裂：应变的烯丙基环丁醇和环丙醇很容易经历如标题重排所描述的环膨胀。该反应通过催化量为1来促进，并且相对于底物范围显示出高耐受性。相应的β-氟螺酮产品以高收率和出色的立体选择性被分离出来。EDG =给电子基团，EWG =吸电子基团。
• Enantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations
  作者：Fedor Romanov-Michailidis、Maria Romanova-Michaelides、Marion Pupier、Alexandre Alexakis

  DOI：10.1002/chem.201406133

  日期：2015.3.27

  the heavier halogens (bromine and iodine) second, the scope and limitations of the halogenative phase‐transfer methodology will be discussed and compared. An extension of the fluorination/semi‐pinacol reaction to the ring‐expansion of five‐membered allylic cyclopentanols will be also described, as well as some preliminary results on substrates prone to desymmetrization will be given. Finally, the present

  本文全文对我们在对映选择性卤化引发的半频哪醇重排中获得的最新结果进行了调查。首先从氟化/半频哪醇反应开始，然后转向较重的卤素（溴和碘），将讨论和比较卤化相转移方法的范围和局限性。还将描述氟化/半频哪醇反应对五元烯丙基环戊醇扩环的扩展作用，并给出了易于脱对称的底物的一些初步结果。最后，本手稿将以规范的氟化/半频哪醇反应的详细机理研究为结尾。我们的机理讨论将基于原位反应进度监控，
• A Mn(<scp>iii</scp>)/TEMPO-co-mediated tandem azidation–1,2-carbon migration reaction of allylic silyl ethers
  作者：Zhi-Min Chen、Zhen Zhang、Yong-Qiang Tu、Ming-Hui Xu、Fu-Min Zhang、Chen-Chen Li、Shao-Hua Wang

  DOI：10.1039/c4cc04707a

  日期：——

  A novel Mn(III)/TEMPO-co-mediated tandem azidation-1,2-carbon migration reaction of allylic silyl ethers with an unactivated C=C bond has been explored, generating alpha-aryl-alkyl beta-azido ketones with an alpha-quaternary stereocenter.

  探索了一种新型的Mn（III）/ TEMPO-co介导的具有未活化C = C键的烯丙基甲硅烷基醚串联叠氮化-1,2-碳迁移反应，产生了具有α -四元立体中心。
• Electrochemical halogenation/semi-pinacol rearrangement of allylic alcohols using inorganic halide salt: an eco-friendly route to the synthesis of β-halocarbonyls
  作者：Chao Chen、Jun-Chen Kang、Chen Mao、Jia-Wei Dong、Yu-Yang Xie、Tong-Mei Ding、Yong-Qiang Tu、Zhi-Min Chen、Shu-Yu Zhang

  DOI：10.1039/c9gc01152h

  日期：——

  An efficient and eco-friendly electrochemical method involving halogenation/semi-pinacol rearrangement of allylic alcohols using inorganic halide salt as the halogen source to synthesize various β-halocarbonyls bearing an all-carbon α-quaternary center under mild reaction conditions has been developed (X = Br, Cl). Stoichiometric oxidants, metal catalysts, and even external electrolytes were avoided

  已开发出一种高效，环保的电化学方法，该方法涉及使用无机卤化物盐作为卤素源，对烯丙醇进行卤化/半频哪醇重排，以在温和的反应条件下合成带有全碳α-季中心的各种β-卤代羰基化合物（X = Br，Cl）。该方法避免了化学计量的氧化剂，金属催化剂，甚至外部电解质。发现整个反应体系与水中各种常见的干扰离子相容，并且对溴离子显示出良好的选择性。此外，可以从模拟废水中高效提取卤素资源，以构建用于合成天然产物（±）-加兰他敏和（±）-Crinamine的关键中间体。此外，
• Copper-Catalyzed Tandem Trifluoromethylation/Semipinacol Rearrangement of Allylic Alcohols
  作者：Zhi-Min Chen、Wei Bai、Shao-Hua Wang、Bin-Miao Yang、Yong-Qiang Tu、Fu-Min Zhang

  DOI：10.1002/anie.201304557

  日期：2013.9.9

  A novel copper‐catalyzed tandem trifluoromethylation/semipinacol rearrangement reaction of allylic alcohols has been achieved under mild conditions. This reaction is valuable for the difunctionalization of alkenes through simultaneous construction of a CCF3 bond and a quaternary carbon center, and could provide a straightforward strategy for the preparation of α‐quaternary β‐trifluoromethyl ketone

  串联跳跃：在温和条件下已实现了一种新型的铜催化的烯丙醇串联三氟甲基化/ semipinacol重排反应。该反应是烯烃的通过C的同时施工的difunctionalization有价值 CF 3键和季碳中心，并且可为α-β季三氟甲基酮衍生物的制备一个简单的策略。