(+)-(7R,E)-hinokiresinol | 96895-25-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (+)-(7R,E)-hinokiresinol
• 英文别名: (+)-(R)-hinokiresinol；trans-hinokiresinol；(-)-hinokiresinol；hinokiresinol；(+)-(7R)-EHR；Nyasol；4-[(1E,3R)-3-(4-hydroxyphenyl)penta-1,4-dienyl]phenol
• CAS: 96895-25-9
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: VEAUNWQYYMXIRB-BOTMBNHJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (R,E)-4,4'-(penta-1,4-diene-1,3-diyl)bis(methoxybenzene) 在 甲基碘化镁 作用下， 以 乙醚 为溶剂， 160.0 ℃ 、20.0 kPa 条件下， 反应 1.0h， 以86%的产率得到(+)-(7R,E)-hinokiresinol
  参考文献：
  名称：

  Iridium-Catalyzed Enantioselective Allylic Vinylation

  摘要：

  The first example of Ir-catalyzed asymmetric substitution reaction with vinyl trifluoroborates is described. The direct reaction between branched, racemic allylic alcohols and potassium alkenyltrifluoroborates proceeded with high site selectivity and excellent enantioselectivity (up to 99%) mediated by an Ir-(P,olefin) complex. This method allows rapid access to various 1,4-dienes or trienes including the biologically active natural products (-)-nyasol and (-)-hinokiresinol.

  DOI：

  10.1021/ja311422z

文献信息

• Structure and Absolute Configuration of Nyasol and Hinokiresinol via Synthesis and Vibrational Circular Dichroism Spectroscopy
  作者：Peter R. Lassen、Dorthe Mondrup Skytte、Lars Hemmingsen、Simon Feldbæk Nielsen、Teresa B. Freedman、Laurence A. Nafie、S. Brøgger Christensen

  DOI：10.1021/np0502995

  日期：2005.11.1

  The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol enables establishment of the absolute configuration of (-)-hinokiresinol, which is concluded to be S. A total

  通过将实验振动圆二色性数据与考虑到八个最低能量构象的第一原理计算进行比较，确定降丽寡糖（+）-nyasol的绝对构型为S。建立的（+）-nyasol绝对构型可以确定（-）-hinokiresinol的绝对构型，该构型最终定为S。已完成hinokiresinol的全合成和拆分，以解决与N偶联的常数的矛盾报道。该分子中双取代双键的乙烯基质子。外消旋的hinokiresinol得到解决。两种对映体均具有相同的抗血浆活性。
• Subunit composition of hinokiresinol synthase controls enantiomeric selectivity in hinokiresinol formation
  作者：Masaomi Yamamura、Shiro Suzuki、Takefumi Hattori、Toshiaki Umezawa

  DOI：10.1039/b918656e

  日期：——

  Asparagus officinalis hinokiresinol synthase (HRS) is composed of two subunits, HRSα and HRSβ. Individually, each subunit forms (E)-hinokiresinol (EHR) from 4-coumaryl 4-coumarate, whereas a mixture of both subunits forms (Z)-hinokiresinol (ZHR) from the same substrate. In this study, we analyzed the enantiomeric compositions of ZHR and EHR formed after incubation of 4-coumaryl 4-coumarate with recombinant subunit proteins, recHRSα and/or recHRSβ, and with naturally occurring A. officinalis ZHR. The enantiomeric composition of ZHR formed by the mixture of recHRSα and recHRSβ was (+)-100% enantiomer excess (e.e.), identical to that of A. officinalis ZHR. In contrast, the enantiomeric compositions of EHR formed by recHRSα and recHRSβ, individually, were (−)-20.6 and (−)-9.0% e.e., respectively. These results clearly demonstrate that the subunit composition of A. officinalis HRS controls not only cis/trans isomerism but also enantioselectivity in hinokiresinol formation.

  天门冬桧醚合成酶（HRS）由 HRSα 和 HRSβ 两个亚基组成。每个亚基单独从 4-香豆酰 4-香豆酸酯中生成（E）-桧烯二酚（EHR），而两个亚基的混合物则从相同的底物中生成（Z）-桧烯二酚（ZHR）。在本研究中，我们分析了 4-香豆素与重组亚基蛋白 recHRSα 和/或 recHRSβ 以及天然 A. officinalis ZHR 培养后形成的 ZHR 和 EHR 的对映体组成。由 recHRSα 和 recHRSβ 混合物形成的 ZHR 对映体组成为对映体过量 (+)-100% (e.e.)，与 A. officinalis ZHR 的对映体组成相同。相比之下，recHRSα 和 recHRSβ 分别形成的 EHR 对映体组成分别为 (-)-20.6% 和 (-)-9.0% e.e.。这些结果清楚地表明，A. officinalis HRS 的亚基组成不仅控制着顺式/反式异构体，还控制着桧脂醇形成过程中的对映体选择性。
• Iridium-Catalyzed Enantioselective Allylic Vinylation
  作者：James Y. Hamilton、David Sarlah、Erick M. Carreira

  DOI：10.1021/ja311422z

  日期：2013.1.23

  The first example of Ir-catalyzed asymmetric substitution reaction with vinyl trifluoroborates is described. The direct reaction between branched, racemic allylic alcohols and potassium alkenyltrifluoroborates proceeded with high site selectivity and excellent enantioselectivity (up to 99%) mediated by an Ir-(P,olefin) complex. This method allows rapid access to various 1,4-dienes or trienes including the biologically active natural products (-)-nyasol and (-)-hinokiresinol.