(S,S)-(-)-4-hydroxy-2-phenyl-3a,4,9,9a-tetrahydro-4,9-[1',2']-benzeno-1H-benz[f]isoindole-1,3(2H)-dione | 354150-90-6

• 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: (S,S)-(-)-4-hydroxy-2-phenyl-3a,4,9,9a-tetrahydro-4,9-[1',2']-benzeno-1H-benz[f]isoindole-1,3(2H)-dione
• 英文别名: (15S)-10-hydroxy-13-phenyl-10,11-dihydro-9H-9,10-[3,4]epipyrroloanthracene-12,14(13H,15H)-dione；4-hydroxy-2-phenyl-3a,4,9,9a-tetrahydro-4,9[1',2']benzeno-1H-benz[f]isoindole-1,3(2H)-dione；(15S,19S)-1-hydroxy-17-phenyl-17-azapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2,4,6,9,11,13-hexaene-16,18-dione
• CAS: 354150-90-6
• 化学式: C₂₄H₁₇NO₃
• 分子量: 367.404
• InChiKey: DESCGYIRGMXULH-CAZKKTPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  57.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-苯基马来酰亚胺 、 蒽酮 在 (1R,2R)-N,N-dimethyl-N'-phthaloyl-1,2-diaminocyclohexane 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以90%的产率得到(S,S)-(-)-4-hydroxy-2-phenyl-3a,4,9,9a-tetrahydro-4,9-[1',2']-benzeno-1H-benz[f]isoindole-1,3(2H)-dione
  参考文献：
  名称：

  简单手性叔胺催化的蒽酮和马来酰亚胺的对映选择性狄尔斯-阿尔德反应

  摘要：

  带有特殊酰亚胺骨架的简单手性叔胺首次成功地用于催化蒽酮和马来酰亚胺的对映选择性D-A反应，具有极高的收率（高达96％）和对映选择性（高达95％ee）。

  DOI：

  10.1016/j.tet.2012.11.011

文献信息

• Asymmetric organocatalytic anthrone additions to activated alkenes
  作者：Alex Zea、Andrea-Nekane R. Alba、Natalia Bravo、Albert Moyano、Ramon Rios

  DOI：10.1016/j.tet.2011.02.032

  日期：2011.4

  Asymmetric organocatalytic additions of anthrones to activated alkenes are discussed. The reaction between anthrone or dithranol and α,β-unsaturated aldehydes is catalyzed by diphenylprolinol trimethylsilyl ether in toluene at −40 °C, giving the Michael adducts with good yields and enantioselectivities. Bifunctional amino-thioureas efficiently catalyze the additions of anthrones to both nitroalkenes and maleimides

  讨论了蒽酮向活化烯烃的不对称有机催化加成反应。在-40°C下，二苯基脯氨醇三甲基甲硅烷基醚在甲苯中催化蒽酮或二乙醇烷与α，β-不饱和醛之间的反应，从而使迈克尔加合物具有良好的收率和对映选择性。双官能氨基硫脲可有效地催化蒽酮向硝基烯烃和马来酰亚胺的添加，并且在室温下的两种情况下均可实现高对映选择性。在硝基烯烃的情况下，仅迈克尔加成发生。蒽酮通常与马来酰亚胺反应生成Diels–Alder环加合物，而二蒽酚则提供迈克尔加成物。
• A chiral analog of the bicyclic guanidine TBD: synthesis, structure and Brønsted base catalysis
  作者：Mariano Goldberg、Denis Sartakov、Jan W Bats、Michael Bolte、Michael W Göbel

  DOI：10.3762/bjoc.12.176

  日期：——

  catalyzes Diels-Alder reactions of anthrones and maleimides (25-30% ee). It also promotes as a strong Bronsted base the retro-aldol reaction of some cycloadducts with kinetic resolution of the enantiomers. In three cases, the retro-aldol products (48-83% ee) could be recrystallized to high enantiopurity (>/=95% ee). The absolute configuration of several compounds is supported by anomalous X-ray diffraction

  从（S）-β-苯丙氨酸开始，可通过脂肪酶催化的动力学拆分轻松获得，通过还原胺化组装手性三胺，最后环化形成标题化合物10。在苯甲酸胍盐的晶体中有六个成员环10的分子中的构象接近于具有在伪轴向位置上的苯基取代基的包膜。未质子化的胍10催化蒽酮和马来酰亚胺的Diels-Alder反应（25-30％ee）。它也促进了一些环加合物的逆醛醇反应作为强布朗斯台德碱，并且具有对映异构体的动力学拆分。在三种情况下，逆醛醇产品（48-83％ee）可以重结晶至高对映体纯度（> / = 95％ee）。几种化合物的绝对构型由异常X射线衍射和化学相关性支持。
• A First Case of Asymmetric Catalysis Induced by Metal-Free Bisoxazolines
  作者：Deniz Akalay、Gerd Dürner、Michael W. Göbel

  DOI：10.1002/ejoc.200800179

  日期：2008.5

  Metal-free bisoxazolines catalyze the Diels–Alder reaction of N-substituted maleimides with anthrone derivatives leading to products in excellent yields and enantioselectivities up to 70 %. A mechanism relying on Bronsted-base catalysis is assumed to be involved with formation of an ion pair between the protonated catalyst and the anthrone enolate, which acts as a diene.(© Wiley-VCH Verlag GmbH & Co. KGaA

  不含金属的双恶唑啉可催化 N-取代马来酰亚胺与蒽酮衍生物的 Diels-Alder 反应，从而产生出色的产率和高达 70% 的对映选择性。假设依赖布朗斯台德碱催化的机制涉及质子化催化剂和作为二烯的蒽酮烯醇化物之间离子对的形成。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany , 2008)
• Chiral primary amino alcohol organobase catalysts for the asymmetric Diels–Alder reactions of anthrones with maleimides
  作者：Jun Kumagai、Teppei Otsuki、U.V. Subba Reddy、Yoshihito Kohari、Chigusa Seki、Koji Uwai、Yuko Okuyama、Eunsang Kwon、Michio Tokiwa、Mitsuhiro Takeshita、Hiroto Nakano

  DOI：10.1016/j.tetasy.2015.10.022

  日期：2015.12

  Simple chiral triethylsilyl-amino alcohol organocatalysts containing a bulky triethylsilyl group on the oxygen atom at the gamma-position were designed and synthesized as new organocatalysts for enantioselective Diels-Alder reactions of anthrones with maleimides to produce chiral hydroanthracene Diels-Alder adducts in up to 99% yield and with up to 94% ee. (c) 2015 Elsevier Ltd. All rights reserved.
• Reversal of enantioselectivity induced by the achiral part of an organocatalyst in a Diels–Alder reaction
  作者：Trupti S. Tawde、Swapnil J. Wagh、Jai V. Sapre、Vaibhav N. Khose、Purav M. Badani、Anil V. Karnik

  DOI：10.1016/j.tetasy.2016.01.002

  日期：2016.2