(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

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (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
• 英文别名: (1R,6S,7R,8R)-7-(1,3-benzodioxol-5-yl)-8-methyl-4-phenylmethoxy-1-prop-2-enylbicyclo[4.2.0]oct-3-ene-2,5-dione
• 化学式: C₂₆H₂₄O₅
• 分子量: 416.474
• InChiKey: AUCIOGMYHRTTBF-RXNHUNJRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  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 various solvent(s) 为溶剂， 生成 (1R,5R,6R,7R)-5-Allyl-7-benzo[1,3]dioxol-5-yl-3-hydroxy-6-methyl-bicyclo[3.2.1]oct-3-ene-2,8-dione
  参考文献：
  名称：

  用相同的原料立体选择性合成三种新木脂素

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)60310-6
• 作为产物：
  描述：

  2-(Benzyloxy)-1,4-benzoquinone 在 四氯化钛 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 (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
  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

• 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.
• 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。