rel-(1R,4aR,9S,9aS,10R)-4a,9,9a,10-tetrahydro-9,10-diphenylspiro[9,10-epoxyanthracene-1(4H),2'-oxiran]-4-one

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: rel-(1R,4aR,9S,9aS,10R)-4a,9,9a,10-tetrahydro-9,10-diphenylspiro[9,10-epoxyanthracene-1(4H),2'-oxiran]-4-one
• 英文别名: (1S,2S,6S,7R,8R)-1,8-diphenylspiro[15-oxatetracyclo[6.6.1.02,7.09,14]pentadeca-4,9,11,13-tetraene-6,2'-oxirane]-3-one
• 化学式: C₂₇H₂₀O₃
• 分子量: 392.454
• InChiKey: YZPLLVYCVKFPKP-UIPNDDLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-氧杂螺[2.5]辛-4,7-二烯-6-酮 、 1,3-二苯基异苯并呋喃 以 苯 为溶剂， 反应 8.5h， 生成 rel-(1R,4aR,9S,9aS,10R)-4a,9,9a,10-tetrahydro-9,10-diphenylspiro[9,10-epoxyanthracene-1(4H),2'-oxiran]-4-one
  参考文献：
  名称：

  Preference for the Diels–Alder addition of dienessynto the O atom in cross-conjugated spirocyclic cyclohexadienones

  摘要：

  In the Diels-Alder reaction, the preferred addition of dienes syn to the O atom in cross-conjugated cyclohexadienones containing an oxa-spiro ring system is observed. The two structures reported here, namely rel-(1R,4aR,9S,9aS,10R)-4a,9,9a,10-tetrahydro-9,10-diphenylspiro[9,10-epoxyanthracene-1(4H),2'-oxiran]-4-one, C27H20O3, and rel-(1R,4aS,9R,9aS,10S)-4a,9,9a,10-tetrahydro-9,10-diphenylspiro[9,10-epoxyanthracene-1(4H),2'-oxetane]-4-one, C28H22O3, are the minor and sole products, respectively, of the reactions of diphenylisobenzofuran with two slightly different cyclohexadienones. These structures differ in the size of the oxa-spiro ring, by one C atom, and in the relative configuration at the spirocyclic ring C atom, leading to some minor conformational differences between the two compounds.

  DOI：

  10.1107/s0108270104015951

文献信息

• Stereoselectivity Control by Oxaspiro Rings during Diels−Alder Cycloadditions to Cross-Conjugated Cyclohexadienones:  The <i>Syn</i> Oxygen Phenomenon
  作者：Katsuo Ohkata、Yukiko Tamura、Brandon B. Shetuni、Ryukichi Takagi、Wataru Miyanaga、Satoshi Kojima、Leo A. Paquette

  DOI：10.1021/ja047027t

  日期：2004.12.1

  parameters were determined for the cycloaddition of 1a and 2a to cyclopentadiene. The rate acceleration profile of solvents was in the order CF(3)CH(2)OH >> CH(3)CN approximately CH(2)Cl(2) for the production of 9a from 1a and CF(3)CH(2)OH >> CH(2)Cl(2) > CH(3)CN for the production of 21a from 2a, respectively. This spread in polarity had no major impact on product distribution, a phenomenon also reflected

  已经研究了在涉及具有不同反应性的二烯的螺环交叉共轭环己二烯酮的 Diels-Alder 加成中操作的非对映面选择性。该研究包括醚系列 1a-c 以及内酯/酮对 2a/2b。在所有情况下，优选的 [4+2] 环加成途径由从 pi 表面顺式键合到氧原子组成。4-取代的-4-甲基-2,5-环己二烯酮（单环系统）也进行了检查，发现它们优先从带有两个基团在4位吸电子更多的表面形成键。确定了 1a 和 2a 环加成生成环戊二烯的动力学参数。溶剂的速率加速曲线的顺序为 CF(3)CH(2)OH >> CH(3)CN 大约 CH(2)Cl(2) 用于从 1a 生产 9a 和 CF(3)CH(2)OH >> CH(2)Cl(2) > CH(3)CN 用于生产21a 分别来自 2a。这种极性分布对产品分布没有重大影响，这一现象也反映在 4-取代-4-甲基-2,5-环己二烯酮在可比条件下的行为中。这些实验事实的理论评估是在