2-Allyl-5-(benzyloxy)-1,4-benzoquinone | 147915-99-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Allyl-5-(benzyloxy)-1,4-benzoquinone
• 英文别名: 2-Phenylmethoxy-5-prop-2-enylcyclohexa-2,5-diene-1,4-dione
• CAS: 147915-99-9
• 化学式: C₁₆H₁₄O₃
• 分子量: 254.285
• InChiKey: MZOQCVVREVIBHB-UHFFFAOYSA-N

物化性质

• 沸点：
  412.8±45.0 °C(predicted)
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Allyl-5-(benzyloxy)-1,4-benzoquinone 在 titanium(IV) isopropylate 、 四氯化钛 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.25h， 生成 (2R,3S)-4-Allyl-7-benzyloxy-2-(3,4-dimethoxy-phenyl)-3-methyl-2,3-dihydro-benzofuran-5-ol
  参考文献：
  名称：

  Regioselective Lewis Acid-Directed Reactions of 2-Alkoxy-5-alkyl-1,4-benzoquinones with Styrenes: Synthesis of Burchellin and Guianin Neolignans

  摘要：

  Reactions of 2-carbomethoxy-5-methoxy-1,4-benzoquinone with (E)-propenylbenzenes promoted by Ti(IV) regio- and stereoselectively yield trans 2-aryl-4-carbomethoxy-7-methoxy-3-methyl-2,3-dihydro-5-benzofuranols. However, the products found in Lewis acid-promoted reactions of 2-alkoxy-5-alkyl-1,4-benzoquinones with (E)-propenylbenzenes depend on the nature of the Lewis acid. Low-temperature reactions with SnCl4 produce rel-(1R,6S,7S,8R)-4-alkoxy-1-alkyl-7-aryl-8-methylbicyclo[4.2.0]oct-5-ene-2,5-diones 21-23 and products derived from them. Allowing the reactions to warm to room temperature results in rel-(2S,3S,3aR)-3a-alkyl-2-aryl-5-hydroxy-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans as mixtures of keto-enol tautomers 26/27 and 28/ 29. With Ti(IV) as promoter, the reactions can be made to produce either 21-23 or the regioisomeric rel-(1S,6R,7R,8S)-4-alkoxy-1-alkyl-8-aryl-7-methylbicyclo[4.2.0]oct-3-ene-2,5-diones 18-20. The ratio of the two depends upon the makeup of the Ti(IV) promoter and the substituents on the propenylbenzene. A mechanistic rationale is presented involving regioselective coordination of the different Lewis acids to the quinone. Thus, SnCl4 binds to the C-1 carbonyl and C-2 alkoxy oxygens, forming a complex possessing a 2-alkoxy-5-alkyl-4-oxa-2,5-cyclohexadienyl carbocation moiety (e.g. 30) which undergoes a thermally allowed 4 pi + 2 pi (5 + 2) cycloaddition with propenylbenzene to give a bicyclo[3.2.1]octenyl carbocation 31; this cation then rearranges to the observed products. On the other hand, the Ti(IV)-promoted reactions give either bicyclo[3.2.1]octenyl carbocation 31 or 34, depending upon reaction conditions, followed by rearrangement. Cyclobutanes 18-20 undergo protic acid rearrangement to give trans 7-alkoxy-4-alkyl-2-aryl-3-methyl-2,3-dihydro-5-benzofuranols 15-17, whereas cyclobutanes 21-23 yield 5-alkyl-7-aryl-3-hydroxy-6-methylbicyclo[3.2.1]oct-3-ene-2,8-diones 24/25. The reactions provide an efficient and stereoselective route to neolignans of the guianin and burchellin classes.

  DOI：

  10.1021/jo00101a017
• 作为产物：
  描述：

  (1R,6S,7R,8R)-1-Allyl-7-benzo[1,3]dioxol-5-yl-4-benzyloxy-8-methyl-bicyclo[4.2.0]oct-3-ene-2,5-dione 在 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 17.0h， 以18%的产率得到2-Allyl-5-(benzyloxy)-1,4-benzoquinone
  参考文献：
  名称：

  Regioselective Lewis Acid-Directed Reactions of 2-Alkoxy-5-alkyl-1,4-benzoquinones with Styrenes: Synthesis of Burchellin and Guianin Neolignans

  摘要：

  Reactions of 2-carbomethoxy-5-methoxy-1,4-benzoquinone with (E)-propenylbenzenes promoted by Ti(IV) regio- and stereoselectively yield trans 2-aryl-4-carbomethoxy-7-methoxy-3-methyl-2,3-dihydro-5-benzofuranols. However, the products found in Lewis acid-promoted reactions of 2-alkoxy-5-alkyl-1,4-benzoquinones with (E)-propenylbenzenes depend on the nature of the Lewis acid. Low-temperature reactions with SnCl4 produce rel-(1R,6S,7S,8R)-4-alkoxy-1-alkyl-7-aryl-8-methylbicyclo[4.2.0]oct-5-ene-2,5-diones 21-23 and products derived from them. Allowing the reactions to warm to room temperature results in rel-(2S,3S,3aR)-3a-alkyl-2-aryl-5-hydroxy-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans as mixtures of keto-enol tautomers 26/27 and 28/ 29. With Ti(IV) as promoter, the reactions can be made to produce either 21-23 or the regioisomeric rel-(1S,6R,7R,8S)-4-alkoxy-1-alkyl-8-aryl-7-methylbicyclo[4.2.0]oct-3-ene-2,5-diones 18-20. The ratio of the two depends upon the makeup of the Ti(IV) promoter and the substituents on the propenylbenzene. A mechanistic rationale is presented involving regioselective coordination of the different Lewis acids to the quinone. Thus, SnCl4 binds to the C-1 carbonyl and C-2 alkoxy oxygens, forming a complex possessing a 2-alkoxy-5-alkyl-4-oxa-2,5-cyclohexadienyl carbocation moiety (e.g. 30) which undergoes a thermally allowed 4 pi + 2 pi (5 + 2) cycloaddition with propenylbenzene to give a bicyclo[3.2.1]octenyl carbocation 31; this cation then rearranges to the observed products. On the other hand, the Ti(IV)-promoted reactions give either bicyclo[3.2.1]octenyl carbocation 31 or 34, depending upon reaction conditions, followed by rearrangement. Cyclobutanes 18-20 undergo protic acid rearrangement to give trans 7-alkoxy-4-alkyl-2-aryl-3-methyl-2,3-dihydro-5-benzofuranols 15-17, whereas cyclobutanes 21-23 yield 5-alkyl-7-aryl-3-hydroxy-6-methylbicyclo[3.2.1]oct-3-ene-2,8-diones 24/25. The reactions provide an efficient and stereoselective route to neolignans of the guianin and burchellin classes.

  DOI：

  10.1021/jo00101a017

文献信息

• Stereoselective syntheses of three different classes of neolignans from the same starting materials
  作者：Thomas A. Engler、Dong (Donna) Wei、Michael A. Letavic

  DOI：10.1016/s0040-4039(00)60310-6

  日期：1993.2

  Lewis Acid catalyzed reactions of 2-alkoxy-5-allyl-1,4-benzoquinones with styrenes can be manipulated to form either the burchellin or guianin neolignans, or 4-allyl-2-aryl-3-methyl-2,3-dihydrobenzofurans.

  路易斯酸催化的2-烷氧基-5-烯丙基-1,4-苯醌与苯乙烯的反应可以形成burchellin或guianin neolignans，或4-烯丙基-2-芳基-3-甲基-2,3-二氢苯并呋喃。
• Regioselective Lewis Acid-Directed Reactions of 2-Alkoxy-5-alkyl-1,4-benzoquinones with Styrenes: Synthesis of Burchellin and Guianin Neolignans
  作者：Thomas A. Engler、Dong Donna Wei、Michael A. Letavic、Keith D. Combrink、Jayachandra P. Reddy

  DOI：10.1021/jo00101a017

  日期：1994.11

  Reactions of 2-carbomethoxy-5-methoxy-1,4-benzoquinone with (E)-propenylbenzenes promoted by Ti(IV) regio- and stereoselectively yield trans 2-aryl-4-carbomethoxy-7-methoxy-3-methyl-2,3-dihydro-5-benzofuranols. However, the products found in Lewis acid-promoted reactions of 2-alkoxy-5-alkyl-1,4-benzoquinones with (E)-propenylbenzenes depend on the nature of the Lewis acid. Low-temperature reactions with SnCl4 produce rel-(1R,6S,7S,8R)-4-alkoxy-1-alkyl-7-aryl-8-methylbicyclo[4.2.0]oct-5-ene-2,5-diones 21-23 and products derived from them. Allowing the reactions to warm to room temperature results in rel-(2S,3S,3aR)-3a-alkyl-2-aryl-5-hydroxy-3-methyl-2,3,3a,6-tetrahydro-6-oxobenzofurans as mixtures of keto-enol tautomers 26/27 and 28/ 29. With Ti(IV) as promoter, the reactions can be made to produce either 21-23 or the regioisomeric rel-(1S,6R,7R,8S)-4-alkoxy-1-alkyl-8-aryl-7-methylbicyclo[4.2.0]oct-3-ene-2,5-diones 18-20. The ratio of the two depends upon the makeup of the Ti(IV) promoter and the substituents on the propenylbenzene. A mechanistic rationale is presented involving regioselective coordination of the different Lewis acids to the quinone. Thus, SnCl4 binds to the C-1 carbonyl and C-2 alkoxy oxygens, forming a complex possessing a 2-alkoxy-5-alkyl-4-oxa-2,5-cyclohexadienyl carbocation moiety (e.g. 30) which undergoes a thermally allowed 4 pi + 2 pi (5 + 2) cycloaddition with propenylbenzene to give a bicyclo[3.2.1]octenyl carbocation 31; this cation then rearranges to the observed products. On the other hand, the Ti(IV)-promoted reactions give either bicyclo[3.2.1]octenyl carbocation 31 or 34, depending upon reaction conditions, followed by rearrangement. Cyclobutanes 18-20 undergo protic acid rearrangement to give trans 7-alkoxy-4-alkyl-2-aryl-3-methyl-2,3-dihydro-5-benzofuranols 15-17, whereas cyclobutanes 21-23 yield 5-alkyl-7-aryl-3-hydroxy-6-methylbicyclo[3.2.1]oct-3-ene-2,8-diones 24/25. The reactions provide an efficient and stereoselective route to neolignans of the guianin and burchellin classes.