6,6-(Ethylenedioxy)heptanal | 142055-97-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,6-(Ethylenedioxy)heptanal
• 英文别名: 5-(2-Methyl-1,3-dioxolan-2-yl)pentanal
• CAS: 142055-97-8
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: JQSSIUJWLJECGG-UHFFFAOYSA-N

物化性质

• 沸点：
  241.3±15.0 °C(Predicted)
• 密度：
  0.991±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6,6-(Ethylenedioxy)heptanal 在 lithium hydroxide 、 叔丁基锂 、 silica gel 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 丙酮 、 正戊烷 、 苯 为溶剂， 反应 1.0h， 生成 ethyl (2-butyl-3-methyl-2-cycloheptenyl)acetate
  参考文献：
  名称：

  The First Tandem [2 + 2] Cycloaddition−Michael Reaction Using Ynolates:  Facile Construction of Substituted Carbocycles

  摘要：

  [GRAPHICS]A tandem [2 + 2] cycloaddition-Michael reaction using ynolate anions followed by decarboxylation produced polysubstituted five-, six-, and seven-membered cycloalkenes.

  DOI：

  10.1021/ol0159928
• 作为产物：
  描述：

  辛-7-烯-2-酮 在 三丁基膦 、 碳酸氢钠 、 对甲苯磺酸 、 臭氧 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 6,6-(Ethylenedioxy)heptanal
  参考文献：
  名称：

  Synthesis of Substituted Cyclooctanols by a Samarium(II) Iodide Promoted 8-Endo Radical Cyclization Process

  摘要：

  Samarium(II) iodide (SmI2) has been employed to promote an efficient 8-endo radical cyclization reaction of a variety of substituted olefinic ketones. Various substituted monocyclic, fused bicyclic, and bridged bicyclic cyclooctanols have been synthesized in fair to excellent yield via this protocol. In addition to delineating the synthetic potential of this reaction, experiments have been conducted to determine the source of reduced, noncyclized byproducts present in this and related SmI2-mediated reactions performed under protic conditions.

  DOI：

  10.1021/jo00090a041

文献信息

• Binuclear Pd(I)–Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes
  作者：Yang Zhang、Sebastian Torker、Michel Sigrist、Nikola Bregović、Paweł Dydio

  DOI：10.1021/jacs.0c09254

  日期：2020.10.21

  is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader

  自 1938 年被发现以来，加氢甲酰化得到了彻底的研究并在工业中得到了广泛的应用（每年超过 107 公吨）。然而，迄今为止，使用成熟的 Rh 或助催化剂精确控制其区域选择性的能力已被证明是难以捉摸的，从而限制了许多具有合成价值的醛的获得。钯催化剂代表了一种有吸引力的替代品，但由于不希望的副加工，它们的使用仍然很少。在这里，我们报告了一种高选择性和异常活性的催化剂系统，该系统由一种新型活化策略驱动，并具有独特的 Pd(I)-Pd(I) 机制，涉及碘化物辅助双核步骤以释放产物。这种方法能够对大范围的烯烃和炔烃（包括敏感的起始材料）进行 β 选择性加氢甲酰化。它的效用在抗肥胖药物利莫那班和抗 HIV 药物 PNU-32945 的合成中得到了证明。在更广泛的背景下，新的机理理解使其他对化学工业具有重要意义的羰基化反应的发展成为可能。
• Asymmetric Synthesis of Cyclic α-Amino Phosphonates Using Masked Oxo Sulfinimines (<i>N</i>-Sulfinyl Imines)
  作者：Franklin A. Davis、Seung H. Lee、He Xu

  DOI：10.1021/jo040127x

  日期：2004.5.1

  Five-, six-, and seven-membered cyclic α-amino phosphonates, amino acid surrogates, are prepared in enantiomerically pure form via the highly diastereomeric addition of metal phosphonates to masked oxo sulfinimines. Hydrolysis of the resulting masked oxo α-amino phosphonates followed by reduction of the intermediate cyclic imino phosphonates affords the title compounds in good yield.

  五，六和七元环状α-氨基膦酸酯（氨基酸替代物）是通过将金属膦酸酯高度非对映异构体加到被掩盖的氧亚磺胺上而制成对映体纯形式的。水解所得的掩蔽的羰基α-氨基膦酸酯，然后还原中间体环状亚氨基膦酸酯，以良好的收率得到标题化合物。
• A novel method for selective dioxolanation of ketones in the presence of aldehydes
  作者：Sunggak Kim、Yong Gil Kim、Deog-il Kim

  DOI：10.1016/s0040-4039(00)92243-3

  日期：1992.4

  Selective dioxolanation of ketones in the presence of aldehydes has been achieved by preferential in situ conversion of aldehydes into 1-silyloxysulfonium salts.

  通过将醛优先地原位转化成1-甲硅烷氧基s盐，已经实现了在醛存在下酮的选择性二恶唑酸化。
• Stereochemical Investigations of Samarium(II) Iodide-Promoted 5-Exo and 6-Exo Ketyl-Olefin Radical Cyclization Reactions
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00109a018

  日期：1995.2

  Samarium(II) iodide (SmI2)-promoted ketyl cyclizations of several substituted, unsaturated ketones, providing various cyclopentyl and cyclohexyl systems, have been investigated. The resulting experiments provide stereochemical insight into these reactions and in addition outline the synthetic potential of these 5-exe and 6-exo radical cyclization processes.
• Structure of Alkaloid 275A, a Novel 1-Azabicyclo[5.3.0]decane from a Dendrobatid Frog, <i>Dendrobates </i><i>l</i><i>ehmanni</i>:  Synthesis of the Tetrahydrodiastereomers
  作者：H. Martin Garraffo、Poonam Jain、Thomas F. Spande、John W. Daly、Tappey. H. Jones、Lance J. Smith、Victor E. Zottig

  DOI：10.1021/np0005098

  日期：2001.4.1

  The principal alkaloid 275A in skins of the Colombian poison frog Dendrobates lehmanni has been identified as the pyrrolo[1,2-alpha ]azepane (1), the first occurrence in nature of this "izidine" system. Tetrahydro-l proved identical to one of the four synthetic diastereomers, 2a-2d, thereby establishing that 1 has the 5Z,10E relative stereochemistry. Alkaloid 1 is often accompanied by other congeners, in particular a 5Z,10Z diastereomer 15, a dihydro analogue 16, and a ketone 17. Such izidines in frogs may arise from dietary ants, as do other classes of izidines.