<1'R-(1'α,2'α,5'α)>-5,7-dimethoxy-6',6'-dimethylspiro<2H-1-benzopyran-2,2'-bicyclo<3.1.1>heptan>-4(3H)-one | 115463-47-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: <1'R-(1'α,2'α,5'α)>-5,7-dimethoxy-6',6'-dimethylspiro<2H-1-benzopyran-2,2'-bicyclo<3.1.1>heptan>-4(3H)-one
• 英文别名: 2,3-dihydro-5,7-dimethoxy-2-(6,6-dimethylbicyclo<3.1.1.>-2-heptylidene)-4H-1-benzopyran-4-one；2,3-dihydro-5,7-dimethoxy-2-(6,6-dimethylbicyclo[3.1.1.]-2-heptylidene)-4H-1-benzopyran-4-one；(1'R,2R,5'S)-5,7-dimethoxy-6',6'-dimethylspiro[3H-chromene-2,2'-bicyclo[3.1.1]heptane]-4-one
• CAS: 115463-47-3
• 化学式: C₁₉H₂₄O₄
• 分子量: 316.397
• InChiKey: CPSYSRAADCPKFU-YARKZXGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <1'R-(1'α,2'α,5'α)>-5,7-dimethoxy-6',6'-dimethylspiro<2H-1-benzopyran-2,2'-bicyclo<3.1.1>heptan>-4(3H)-one 在 palladium on activated charcoal 吡啶 、 盐酸 、 氢气 、 溴 作用下， 以 二氯甲烷 为溶剂， 生成 (1'R,2R,4S,5'S)-6,8-dibromo-5,7-dimethoxy-6',6'-dimethyl-4-(2-methylpropyl)spiro[3,4-dihydrochromene-2,2'-bicyclo[3.1.1]heptane]
  参考文献：
  名称：

  罗布二甲醚A和B二甲醚的全合成

  摘要：

  Synthes des composes du titre a partir de (+)-nopinone et de dimethoxy-2',4' hydroxy-6' acetophenone

  DOI：

  10.1021/ja00223a062
• 作为产物：
  描述：

  2-羟基-4,6-二甲氧基苯乙酮 在 四氢吡咯 、 potassium carbonate 作用下， 以 乙醇 、 水 、 苯 为溶剂， 生成 <1'R-(1'α,2'α,5'α)>-5,7-dimethoxy-6',6'-dimethylspiro<2H-1-benzopyran-2,2'-bicyclo<3.1.1>heptan>-4(3H)-one
  参考文献：
  名称：

  罗布二甲醚A和B二甲醚的全合成

  摘要：

  Synthes des composes du titre a partir de (+)-nopinone et de dimethoxy-2',4' hydroxy-6' acetophenone

  DOI：

  10.1021/ja00223a062

文献信息

• One-pot synthesis of precocene I and II and a formal synthesis of robustadial A and B via 2-phenyl-4<i>H</i>-1,3,2-benzodioxaborin
  作者：Suzanne Bissada、Cheuk K. Lau、Michael A. Bernstein、Claude Dufresne

  DOI：10.1139/v94-237

  日期：1994.8.1

  The reaction of a phenol, and α,β-unsaturated aldehyde, and phenylboronic acid yields a 2-phenyl-4H-1,3,2-benzodioxaborin. Upon heating, this compound decomposes to an orthoquinone-methide intermediate, which undergoes an electrocyclization reaction to a chromene ring system. This method has been applied to the synthesis of precocenes I and II and the robustadial A and B.

  苯酚、α,β-不饱和醛和苯硼酸的反应产生2-苯基-4H-1,3,2-苯并二氧硼杂环。加热后，该化合物分解为一个邻醌甲烯中间体，该中间体经历电环化反应形成一个咔啉环系统。这种方法已应用于合成早生素I和II以及强健二烯醇A和B。
• The total synthesis of robustadial A and B dimethyl ethers
  作者：Robert G. Salomon、Kasturi. Lal、Samuel M. Mazza、Eugene A. Zarate、Wiley J. Youngs

  DOI：10.1021/ja00223a062

  日期：1988.7

  Synthese des composes du titre a partir de (+)-nopinone et de dimethoxy-2',4' hydroxy-6' acetophenone

  Synthes des composes du titre a partir de (+)-nopinone et de dimethoxy-2',4' hydroxy-6' acetophenone
• The Synthesis of (-)-Robustadial A and Some Analogues.
  作者：Inger Reidun Aukrust、Lars Skattebøl、Otto Dahl、Georg Hvistendahl、Markku Leskelä、Mika Polamo、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0132

  日期：——

  The naturally occurring chroman derivative, robustadial A, and several analogues have been prepared by a four-step synthesis starting from phloroglucinol. The synthetic scheme involves as the first step a Friedel-Crafts condensation of an alpha,beta-unsaturated acid derivative with phloroglucinol to the corresponding chromanone. The isobutyl group at the 4-position was introduced with methallylzine bromide followed by hydrogenation, carried out as a one-pot reaction. Finally, both aldehyde functions were attached using dichloromethyl methyl ether and titanium tetrachloride. Optically pure 6,6-dimethylbicyclo[3.1.1]heptan-2-ylidene-acetic acid, needed for the synthesis of robustadial, was prepared from (-)-nopol by two consecutive oxidations in 77% overall yield.
• Stereoselective Synthesis Of Dimethylrobustadials
  作者：Marek Majewski、Nicholas M. Irvine、Gary W. Bantle

  DOI：10.1021/jo00101a031

  日期：1994.11

  A stereoselective synthesis of the methyl ethers of robustadials A and B (24) is described. The crucial step is the amine-catalyzed cyclization of the enone 8b which leads to the products 9b and 10b with high diastereoselectivity. The choice of the amine catalyst has a strong influence on the selectivity (i.e. on the ratio of trans and cis products 9b:10b); the amine must have an optimum pK(b) value. The aromatic synthon and the terpene synthon of robustadials are joined via a Prins reaction of a substituted benzaldehyde (3b) with beta-pinene (4). The reaction is strongly dependent on electronic effects, and the choice of substituents on the aromatic ring is critical. The use of (1S)-(-)-beta-pinene ensures the synthesis of enantiomerically pure compounds.
• SALOMON, ROBERT G.;MAZZA, SAMUEL M.;LAL, KASTURI, J. ORG. CHEM., 54,(1989) N, C. 1562-1570
  作者：SALOMON, ROBERT G.、MAZZA, SAMUEL M.、LAL, KASTURI

  DOI：——

  日期：——