1-Formyl-1-(3-butenyl)cyclohexane | 127827-62-7

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: 1-Formyl-1-(3-butenyl)cyclohexane
• 英文别名: 1-But-3-enylcyclohexane-1-carbaldehyde
• CAS: 127827-62-7
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: UZCDXCVHKPCZIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Formyl-1-(3-butenyl)cyclohexane 在 copper diacetate 、 水 、 氧气 、 palladium dichloride 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 以62%的产率得到1-Formyl-1-(3-oxobutyl)cyclohexane
  参考文献：
  名称：

  亚化学计量的乙酸铜可方便地进行Wacker氧化

  摘要：

  描述了使用亚化学计量的量的Cu（OAc）2作为氧化还原穿梭试剂将末端烯烃的Wacker氧化修饰为甲基酮的方法。尽管减少了铜盐的含量，但是改进的方法通常还是高产率的并且方便。重要的是，在有问题的情况下，该条件抑制了在含丙酮化物的底物（+）- 5的氧化过程中的酸性水解。

  DOI：

  10.1016/s0040-4039(98)01992-3
• 作为产物：
  描述：

  环己甲酸甲酯 在 正丁基锂 、 二异丁基氢化铝 、 二异丙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 10.0h， 生成 1-Formyl-1-(3-butenyl)cyclohexane
  参考文献：
  名称：

  调节烷氧基自由基从环化到 1,2-甲硅烷基转移的反应性：β-取代环醇的立体选择性合成

  摘要：

  在此，我们报告了一种非对映选择性构建β-取代的环戊醇和环丁醇的激进策略。反应的成功归因于在烷氧基环化为烯烃时有利的自由基 1,2-甲硅烷基转移。该反应显示出广泛的底物范围和广泛的官能团耐受性。该方法的合成潜力在克级反应和各种螺环化合物的简便合成中得到了证明。

  DOI：

  10.1021/acs.orglett.2c00428

文献信息

• Photoreductive cyclization of unsaturated aldehydes : An easy access to spiranic molecules
  作者：J. Cossy、J.P. Pete、C. Portella

  DOI：10.1016/s0040-4039(00)70697-6

  日期：1989.1

  The photoreductive cyclization of ω-unsaturated aldehydes is an efficient process which leads to substituted cycloalkanols. This process is used as a convenient approach to spiranic molecules.

  ω-不饱和醛的光还原环化是导致取代的环烷醇的有效方法。此过程用作螺环分子的便捷方法。
• Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers
  作者：Gary A. Molander、Kimberly O. Cameron

  DOI：10.1021/jo00074a018

  日期：1993.10

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.
• Selective mono- and polymethylene homologations of copper reagents using (iodomethyl)zinc iodide
  作者：AchyuthaRao Sidduri、Michael J. Rozema、Paul Knochel

  DOI：10.1021/jo00062a010

  日期：1993.5

  A wide range of unsaturated aryl-, alkenyl-, alkynylcopper compounds can be selectively homologated by a methylene unit using (iodomethyl)zinc iodide or bis(iodomethyl)zinc. These reactions allow the generation of mixed allylic zinc-copper compounds which can be efficiently trapped with carbonyl compounds. An application to a general preparation of functionalized alpha-methylene-gamma-butyrolactones is described. The homologation of alkynylcoppers with (iodomethyl)zinc iodide allows a one-pot preparation of propargylic copper reagents which in the presence of a carbonyl compound provide various homopropargylic alcohols in excellent yields. In the absence of an electrophile, a clean quadruple methylene homologation of alkynylcoppers occurs to furnish dienic copper reagents. The homologation of other types of copper reagents is also possible, and carbanions at the alpha-position to amines as well as homoenolates of aldehydes or ketones can also be prepared by this method.
• Convenient Wacker oxidations with substoichiometric cupric acetate
  作者：Amos B. Smith、Young Shin Cho、Gregory K. Friestad

  DOI：10.1016/s0040-4039(98)01992-3

  日期：1998.11

  A modification of the Wacker oxidation of terminal olefins to methyl ketones using substoichiometric amounts of Cu(OAc)2 as a redox shuttle reagent is described. The modified procedure is generally high yielding despite reduced levels of copper salt and convenient. Importantly, in a problematic case, the conditions suppressed acidic hydrolysis during oxidation of substrate (+)-5 containing an acetonide

  描述了使用亚化学计量的量的Cu（OAc）2作为氧化还原穿梭试剂将末端烯烃的Wacker氧化修饰为甲基酮的方法。尽管减少了铜盐的含量，但是改进的方法通常还是高产率的并且方便。重要的是，在有问题的情况下，该条件抑制了在含丙酮化物的底物（+）- 5的氧化过程中的酸性水解。
• Tuning the Reactivity of Alkoxyl Radicals from Cyclization to 1,2-Silyl Transfer: Stereoselective Synthesis of β-Substituted Cycloalcohols
  作者：Xingyi He、Yunlong Zhao、Zeguo Zhang、Xiao Shen

  DOI：10.1021/acs.orglett.2c00428

  日期：2022.3.18

  Herein, we report a radical strategy for diastereoselective construction of β-substituted cyclopentanols and cyclobutanols. The success of the reaction is attributed to the favorable radical 1,2-silyl transfer over the cyclization of alkoxy radicals to the olefins. The reaction shows broad substrate scope and wide functional-group tolerance. The synthetic potential of the methodology was demonstrated

  在此，我们报告了一种非对映选择性构建β-取代的环戊醇和环丁醇的激进策略。反应的成功归因于在烷氧基环化为烯烃时有利的自由基 1,2-甲硅烷基转移。该反应显示出广泛的底物范围和广泛的官能团耐受性。该方法的合成潜力在克级反应和各种螺环化合物的简便合成中得到了证明。