2-allyl-3-ethylenedioxy-2-methylcyclohexanone | 474956-27-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-allyl-3-ethylenedioxy-2-methylcyclohexanone
• 英文别名: 6-methyl-6-prop-2-enyl-1,4-dioxaspiro[4.5]decan-7-one
• CAS: 474956-27-9
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: ZZGPKBLZRQSHNV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.06
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-allyl-3-ethylenedioxy-2-methylcyclohexanone 在 dimethyl sulfide borane 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 30.5h， 生成 1,3-bis(ethylenedioxy)-2-(1-iodopropyl)-2-methylcyclohexane
  参考文献：
  名称：

  Asymmetric construction of novel bicyclo[4.4.0] and [4.3.0]ring systems via intramolecular Horner–Wadsworth–Emmons reactions

  摘要：

  Novel perhydro-indanones and -naphthalenones having a quaternary stereogenic carbon and tetrasubstituted olefinic linkage were prepared via asymmetric intramolecular Horner-Wadsworth-Emmons reactions. The optically active binaphthyl phosphonates were connected with the 2-substituted cyclopenta- or cyclohexa-1,3-dione through the linker arm and the successive base treatment of the products with diethylzinc led to cyclization reactions with concomitant differentiation of diastereotopic carbonyl groups to afford the non-racemic title compounds in good enantiomeric excess. The absolute structure of the cyclized product was determined by X-ray analysis of its derived bromide. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00177-5
• 作为产物：
  描述：

  2-甲基-1,3-环己二酮 在 三氟化硼乙醚 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 2-allyl-3-ethylenedioxy-2-methylcyclohexanone
  参考文献：
  名称：

  Asymmetric construction of novel bicyclo[4.4.0] and [4.3.0]ring systems via intramolecular Horner–Wadsworth–Emmons reactions

  摘要：

  Novel perhydro-indanones and -naphthalenones having a quaternary stereogenic carbon and tetrasubstituted olefinic linkage were prepared via asymmetric intramolecular Horner-Wadsworth-Emmons reactions. The optically active binaphthyl phosphonates were connected with the 2-substituted cyclopenta- or cyclohexa-1,3-dione through the linker arm and the successive base treatment of the products with diethylzinc led to cyclization reactions with concomitant differentiation of diastereotopic carbonyl groups to afford the non-racemic title compounds in good enantiomeric excess. The absolute structure of the cyclized product was determined by X-ray analysis of its derived bromide. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00177-5

文献信息

• High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates
  作者：Brian Stoltz、Nolan McDougal、Scott Virgil

  DOI：10.1055/s-0030-1258094

  日期：2010.7

  The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a nonpolar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard ­reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto ester derived and an α-phenyl cyclohexanone-­derived enol carbonate.

  利用高通量筛选技术优化了钯催化烯醇稳定烯醇碳酸盐不对称脱羧烷基化反应的反应条件。将标准反应条件改为非极性反应溶剂和缺电子的 PHOX 衍生物作为配体后，酮保护的 1,3-二酮衍生烯醇碳酸酯烷基化反应的对映体选择性从 28% ee 提高到 84%ee。δ-酮酯衍生的烯醇碳酸酯和δ-苯基环己酮衍生的烯醇碳酸酯的对映体选择性也有类似的改善。