1-allyl-4-tert-butyl-cyclohexanecarbonitrile | 53188-69-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1-allyl-4-tert-butyl-cyclohexanecarbonitrile
• 英文别名: (1S, 4S)-1-alllyl-4-(tert-butyl)cyclohexanecarbonitrile
• CAS: 53188-69-5
• 化学式: C₁₄H₂₃N
• 分子量: 205.343
• InChiKey: VYHQUIIFSHMYEI-XBXGTLAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  23.79
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-allyl-4-tert-butyl-cyclohexanecarbonitrile 在 二异丁基氢化铝 作用下， 生成 1-Allyl-4-tert-butyl-cyclohexanecarbaldehyde
  参考文献：
  名称：

  Stereochemical aspects of the Claisen rearrangement of allyl vinyl ethers

  摘要：

  DOI：

  10.1021/jo00889a019
• 作为产物：
  描述：

  4-叔丁基环己基甲酸 在 氯化亚砜 、 碘 、 三乙胺 、 亚磷酸三乙酯 作用下， 生成 1-allyl-4-tert-butyl-cyclohexanecarbonitrile
  参考文献：
  名称：

  Rearrangements of Substituted 3-Aza-1,2,5-hexatrienes. 3. The Scope and Versatility of an Extremely Mild 3-Aza-Cope Reaction

  摘要：

  An investigation of the [3,3]-sigmatropic reaction of substituted 3-aza-1,2,5-hexatrienes to give 4-pentenenitriles is presented. This reaction has been found to occur under a wide variety of reactions conditions (10 are reported) starting from readily available N-allylamides. In contrast to other 3-aza-Cope reactions, this process occurs at room temperature, under essentially neutral conditions, allowing for the facile preparation of substituted nitrile products in moderate to excellent yields. The scope and versatility of this reaction are demonstrated by its use on a wide variety of substrates, including nitrogen- and oxygen-substituted amides. The rearrangements of cis- and trans-4-tert-butyl-N-allylcyclohexanecarboxamides 16a and 16b are reported and were found to give a ratio of axial to equatorial (A:E) products consistent with A:E ratios found for other related sigmatropic reactions. The stereochemical requirements for this reaction appear to be similar to other [3,3]-rearrangements even though the transition state for this rearrangement is most likely neither boat nor chairlike.

  DOI：

  10.1021/jo951587g

文献信息

• Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles
  作者：Xun Yang、Dinesh Nath、Michael R. Gau、Omar W. Steward、Fraser F. Fleming

  DOI：10.1002/anie.201704028

  日期：2017.6.12

  sulfone–metal exchange is described. Treating substituted 2‐pyridylsulfonylacetonitriles with either BuLi or Bu3MgLi generates metalated nitriles that efficiently intercept a variety of electrophiles to afford quaternary nitriles. The 2‐pyridylsulfone is critical for the sulfone–metal exchange because chelation anchors the organometallic proximal to the electrophilic, tetrasubstituted sulfone to override

  描述了第一次一般的砜-金属交换。用BuLi或Bu 3 MgLi处理取代的2-吡啶基磺酰基乙腈会生成金属化的腈，该腈可有效拦截各种亲电试剂，从而生成季腈。2-吡啶基砜对于砜与金属的交换至关重要，因为螯合将有机金属锚定在亲电子的四取代砜的近端，以克服复合物引起的去质子化。用温和的碱（K 2 CO 3或DBU）烷基化2-吡啶磺酰基乙腈，然后进行砜-金属交换和烷基化，通过三个烷基化作用快速组装季腈，其中只有一个需要有机金属试剂。
• Cyclic Nitriles:  Diastereoselective Alkylations
  作者：Fraser F. Fleming、Subrahmanyam Gudipati、Zhiyu Zhang、Wang Liu、Omar W. Steward

  DOI：10.1021/jo0501184

  日期：2005.5.1

  Diastereoselective alkylations of metalated conformationally locked 4-tert-butylcyclohexanecarbonitrile are highly diastereoselective with magnesium and copper counterions but only modestly diastereoselective with lithium as the counterion. Selective generation of diverse metalated nitriles is readily achieved through bromine−magnesium, −copper, and −lithium exchange reactions of the corresponding

  金属化的构象锁定的4-叔丁基环己烷甲腈的非对映选择性烷基化与镁和铜抗衡离子具有很高的非对映选择性，而仅以锂作为抗衡离子具有适度的非对映选择性。通过相应溴腈的溴-镁，-铜和-锂交换反应，或者对于锂，通过用二乙酰胺锂使母体腈去质子化，可以轻松实现多种金属化腈的选择性生成。总的来说，高烷基化立体选择性与C-金属腈的保持性烷基化相关，而N-锂化的腈具有适度的选择性，在相应的轴向和赤道亲电轨迹中反映出最小的空间差异。