6-[(2-Methoxyethoxy)methoxy]cyclohex-2-EN-1-one | 390818-21-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-[(2-Methoxyethoxy)methoxy]cyclohex-2-EN-1-one
• 英文别名: 6-(2-methoxyethoxymethoxy)cyclohex-2-en-1-one
• CAS: 390818-21-0
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: MSYWSVVZCBABGI-UHFFFAOYSA-N

物化性质

• 沸点：
  292.0±40.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-[(2-Methoxyethoxy)methoxy]cyclohex-2-EN-1-one 在 Pd-BaSO₄ 、 氢气 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 生成
  参考文献：
  名称：

  在硬碳亲核试剂1,2-加成到C（6）-杂原子取代的环己烯酮中的非对映选择性的不寻常试剂控制。

  摘要：

  [反应：见正文]在C（6）-杂环取代的环己烯酮的硬碳亲核试剂的1,2-加成反应中，发现了令人惊讶且对合成有用的抗衡离子依赖性非对映选择性逆转。通常，尽管发现了一些例外情况，但格氏试剂将syn添加到C（6）-取代基中，而Li试剂添加了抗氧化剂。选择性可以在一些情况下通过溶剂和/或助溶剂适当选择而增加。

  DOI：

  10.1021/ol016673j
• 作为产物：
  描述：

  2-甲氧基乙氧基甲基氯 、 (+)-6-hydroxycyclohexen-2-one 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以65%的产率得到6-[(2-Methoxyethoxy)methoxy]cyclohex-2-EN-1-one
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r

文献信息

• Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis
  作者：Sang-phyo Hong、Harriet A. Lindsay、Tripura Yaramasu、Xiaowei Zhang、Matthias C. McIntosh

  DOI：10.1021/jo010752r

  日期：2002.4.1

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.
• Unusual Reagent Control of Diastereoselectivity in the 1,2-Addition of Hard Carbon Nucleophiles to C₆-Heteroatom Substituted Cyclohexenones
  作者：Harriet A. Lindsay、Catherine L. Salisbury、Wally Cordes、Matthias C. McIntosh

  DOI：10.1021/ol016673j

  日期：2001.12.1

  text] A surprising and synthetically useful counterion-dependent reversal of diastereoselectivity was found in 1,2-additions of hard carbon nucleophiles to C(6)-heterosubstituted cyclohexenones. In general, Grignard reagents added syn to the C(6)-substituent and Li reagents added anti, although some exceptions were found. Selectivities could be increased in some cases by appropriate choice of solvent and/or

  [反应：见正文]在C（6）-杂环取代的环己烯酮的硬碳亲核试剂的1,2-加成反应中，发现了令人惊讶且对合成有用的抗衡离子依赖性非对映选择性逆转。通常，尽管发现了一些例外情况，但格氏试剂将syn添加到C（6）-取代基中，而Li试剂添加了抗氧化剂。选择性可以在一些情况下通过溶剂和/或助溶剂适当选择而增加。