6-allyl-3-isobutoxy-2-cyclohexen-1-one | 40649-34-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-allyl-3-isobutoxy-2-cyclohexen-1-one
• 英文别名: 2-Cyclohexen-1-one, 3-(2-methylpropoxy)-6-(2-propenyl)-；3-(2-methylpropoxy)-6-prop-2-enylcyclohex-2-en-1-one
• CAS: 40649-34-1
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: UYXVIFHCSJABPM-UHFFFAOYSA-N

物化性质

• 熔点：
  37-38 °C
• 沸点：
  95-100 °C(Press: 0.4 Torr)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-allyl-3-isobutoxy-2-cyclohexen-1-one 在 lithium aluminium tetrahydride 、 MoO5*pyridine*HMPA 、 乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 49.92h， 生成 4-Allyl-4-methylsulfanylmethoxy-cyclohex-2-enone
  参考文献：
  名称：

  Some Aspects of Palladium-Catalyzed Cycloalkenylation:  Developments of Environmentally Benign Catalytic Conditions and Demonstration of Tandem Cycloalkenylation

  摘要：

  The influences of catalysts, substituent groups, and solvents on the palladium-catalyzed cycloalkenylation of cross-conjugated silyl enol ethers of 2-tert-butyldimethylsiloxy-5-(2-propenyl)-1,3-cyclohexadiene derivatives have been investigated. The catalytic reaction proceeded smoothly, even in aqueous media. The product ratios were influenced by the structure of substrates as well as solvents. In addition, it was found that the reaction is applicable to a tandem cyclization for the construction of cedrane skeleton.

  DOI：

  10.1021/jo011169d
• 作为产物：
  描述：

  1,3-环己二酮 在 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 6-allyl-3-isobutoxy-2-cyclohexen-1-one
  参考文献：
  名称：

  双环[3.3.1]壬三酮向四氢喹啉-2(1H)-one系统的独特骨架重排

  摘要：

  据报道，在 TsOH 存在下，由双环 [3.3.1] 壬三酮系统和氨基醇意外形成 4-羟基四氢喹啉-2(1H)-one。通过DFT计算研究了这种转变的机制。该反应为高度官能化的 4-羟基四氢喹啉-2(1H)-酮的合成提供了一个入口。

  DOI：

  10.1055/s-0037-1610187

文献信息

• Diastereoselective Formal Total Synthesis of the DNA Polymerase α Inhibitor, Aphidicolin, Using Palladium-Catalyzed Cycloalkenylation and Intramolecular Diels−Alder Reactions
  作者：Masahiro Toyota、Masato Sasaki、Masataka Ihara

  DOI：10.1021/ol034027+

  日期：2003.4.1

  [structure: see text] A novel diastereoselective formal synthesis of aphidicolin has been achieved by exploiting a unique characteristic of a bicyclo[3.2.1]octane prepared by employing a palladium-catalyzed cycloalkenylation process.

  [结构：见正文]通过利用钯催化的环烯基化工艺制备的双环[3.2.1]辛烷的独特特性，实现了一种新型的非对映选择性的蚜虫二烯合成。
• Synthesis of β-chloro, β-bromo, and β-iodo α,β-unsaturated ketones
  作者：Edward Piers、John R. Grierson、Cheuk Kun Lau、Isao Nagakura

  DOI：10.1139/v82-033

  日期：1982.1.15

  A new, efficient method for the preparation of β-chloro, β-bromo, and β-iodo α,β-unsaturated ketones is described. The method involves the reaction of β-diketones or α-hydroxymethylenecycloalkanones with triphenylphosphine dihalides in the presence of triethylamine. With the dichloride and dibromide reagents, the reactions are conveniently carried out in benzene at room temperature, while with triphenylphosphine diiodide the reactions are best performed in refluxing acetonitrile (β-diketones) or in acetonitrile–hexamethylphosphoramide (α-hydroxymethylenecycloalkanones). The reaction of triphenylphosphine diiodide – triethylamine with a series of 4-alkyl-1,3-cyclohexanediones provides mainly or exclusively (depending on the size of the alkyl group) 6-alkyl-3-iodo-2-cyclohexen-1-ones, while reaction of this reagent with 2-hydroxymethylenecyclohexanone and 2-hydroxymethylenecyclopentanone affords stereoselectively and regioselectively (E)-2-iodomethylenecyclohexanone and (E)-2-iodomethylenecyclopentanone, respectively.

  描述了一种制备β-氯、β-溴和β-碘α，β-不饱和酮的新的高效方法。该方法涉及β-二酮或α-羟甲基环戊酮与三苯基膦二卤化物在三乙胺存在下的反应。对于二氯化物和二溴化物试剂，反应通常在苯中室温下进行，而对于三苯基膦二碘化物，最好在回流的乙腈（β-二酮）或乙腈-六甲基磷酰胺（α-羟甲基环戊酮）中进行。三苯基膦二碘化物-三乙胺与一系列4-烷基-1,3-环己二酮的反应主要或仅产生（取决于烷基的大小）6-烷基-3-碘-2-环己烯-1-酮，而该试剂与2-羟甲基环己酮和2-羟甲基环戊酮的反应分别选择性地产生（E）-2-碘甲基环己酮和（E）-2-碘甲基环戊酮。
• Formal Total Synthesis of Platencin
  作者：Georgy N. Varseev、Martin E. Maier

  DOI：10.1002/anie.200900447

  日期：2009.5.4

  The right bicycle: A concise formal synthesis of platencin was based on an efficient oxygen‐mediated palladium‐catalyzed cycloalkenylation of 1 to form a bicyclo[3.2.1]octane, and a deoxygenative rearrangement of tosylhydrazone 2 to construct the bicyclo[2.2.2]octane 3. The total yield of the core structure 4 of platencin was 17.5 % for 13 steps from a commercially available compound. Ts=p‐toluenesulfonyl

  正确的自行车：基于有效的氧介导的钯催化的环烯基化1形成双环[3.2.1]辛烷，以及甲苯磺酰2 2的脱氧重排以构建双环[2.2.2 ]，简洁而正式地合成了Platencin。]辛烷3。从市售化合物获得的13个步骤中，稿台素核心结构4的总产率为17.5％。Ts =对甲苯磺酰基，TBS =叔丁基二甲基甲硅烷基，Piv =新戊酰基。
• The synthesis of aspidosperma alkaloids containing a functional group at C-18; the total synthesis of (±)-N,O-diacetylcylindrocarpinol, (±)-cylindrocarine, (±)-cylindrocarpine, (±)-cylindrocarpidine, and (±)-20-allyl-20-desethyl-20-epiaspidospermine
  作者：G. Lawton、J.E. Saxton、A.J. Smith

  DOI：10.1016/0040-4020(77)80177-4

  日期：1977.1

  The first total synthesis of (±)-N,O-diacetylcylindrocarpinol 49, (±)-cylindrocarine 51, (±)-cylindrocarpidine 1, and (±)-cylindrocarpine 52, starting from pent-4-enal and proceeding via the ketones 12 and 40, is described. The stereoisomenc ketones 20 and 41 were used as intermediates in a parallel synthesis of (±)-20-allyl-20-desethyl-20-epiaspidospermine 47.

  第一个全合成的（±）-N，O-二乙酰基cylindrocarpinol 49，（±）-cylindrocarine 51，（±）-cylindrocarpidine 1和（±）-cylindrocarpine 52从五元四烯醛开始并通过酮进行。描述图12和40。立体异构体酮20和41用作（±）-20-烯丙基-20-去乙基20-表哌啶子亚胺47的平行合成中的中间体。
• One-Pot Assembly of Tricyclo[6.2.1.0^1,6]undecan-4-one and Related Polycyclic Compounds by Tandem Electroreductive Cyclization
  作者：Masahiro Toyota、Andivelu Ilangovan、Yoshitomo Kashiwagi、Masataka Ihara

  DOI：10.1021/ol0484660

  日期：2004.9.1

  Electroreductive tandem cyclization of 4-allyl-4-(2-bromoprop-2-en-1-yl)cyclohex-2-en-1-one to tricyclo[6.2.1.0(1,6)]undecan-4-one has been demonstrated. This protocol represents an attractive alternative to conventional tandem radical cyclization.