山藿香素 | 51918-98-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: 山藿香素
• 中文别名: 1-哌嗪乙酸,a-(4-氰基苯基)-4-[(1,1-二甲基乙氧基)羰基]-
• 英文名称: teucvin
• 英文别名: mallotucin A；(1S,5'S,8S,9R,10R)-5'-(furan-3-yl)-10-methylspiro[2-oxatricyclo[6.3.1.04,12]dodec-4(12)-ene-9,3'-oxolane]-2',3-dione
• CAS: 51918-98-0
• 化学式: C₁₉H₂₀O₅
• 分子量: 328.365
• InChiKey: XJRMFKRYVTYFPN-UISQBHBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  65.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  山藿香素 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 以 四氯化碳 为溶剂， 以54 %的产率得到
  参考文献：
  名称：

  五环19-正环烷烃的对映选择性和集体全合成

  摘要：

  我们在此报道了七种五环 19- nor -clerodane 二萜类化合物的集体不对称全合成，即 (+)-teucvin (+)-cracroson A、(+)-cracroson E、(+)-montanin A、(+)-teucvisin C、(+)-teucrin A 和 (+)-2-羟基 teuscorolide。镱催化的 4-甲基-2-吡喃酮与手性 C5 取代的环己-1,3-二烯醇甲硅烷基醚的不对称逆电子需求狄尔斯-阿尔德反应是该合成的关键特征，它提供了常见的顺式反应-十氢化萘中间体，具有五个连续立体中心，具有优异的产率和立体选择性。从这种多样化的中间体，分别通过十三步和十八步实现了(+)-teucvin和(+)-2-羟基teuscorolide的全合成。通过后期氧化态调整，从 (+)-teucvin 衍生出另外五种五环 19- nor -clerodanes。

  DOI：

  10.1039/d3sc04335e
• 作为产物：
  描述：

  (12S,20S)-7α-Acetoxy-20-O-acetyl-6,18;15,16-diepoxy-19-norneoclerodane-4(18),5,13(16),14-tetraene 20,12-hemiacetal 在 chromium trioxide-pyridine complex 、 硫酸 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 5.0h， 生成 山藿香素
  参考文献：
  名称：

  Transformation of neoclerodane diterpenoids into 19-norneoclerodane derivatives

  摘要：

  The neoclerodane diterpenoid eriocephalin (1) was transformed into its 19-nor derivatives 3 and 4 by reaction with potassium tert-butoxide in THF, whereas with the same treatment compound 6 yielded only the transacetylation derivative 7. These results indicated that 19-acetoxy-4-alpha,18-epoxy-7-alpha-hydroxy-6-oxoneoclerodane derivatives are transformed into the corresponding 19-nor compounds in a retroaldol reaction by loss of the C-19 carbon as formaldehyde followed by opening of the oxirane ring and intramolecular attack by a C-18 alkoxide on the carbonyl C-6 carbon atom, giving the allylic hemiacetal 3, which is easily dehydrated to the furanic derivative 4. Compound 4 was transformed into the alpha,beta-unsaturated gamma,delta-enol gamma-lactone 8 by an oxidation reaction with atomspheric oxygen in chloroform solution. Alternatively, it gave the alpha,beta-unsaturated gamma-lactone 11 under acid catalysis. These reactions allowed the partial syntheses of the naturally occurring diterpenoids teuscorolide (9) and teucvin (12) and are of interest for chemical transformations of substances of this kind.

  DOI：

  10.1021/jo00023a027

文献信息

• The absolute stereochemistry of some clerodane diterpenoids from Teucrium species
  作者：Martin Martinez-Ripoll、Jose Fayos、Benjamin Rodriguez、Maria C. Garcia-Alvarez、Giuseppe Savona、Franco Piozzi、Mariapia Paternostro、James R. Hanson

  DOI：10.1039/p19810001186

  日期：——

  The absolute configurations of 19-acetylgnaphalin, and another diterpenoid from T. gnaphalodes, probably identical with teucrin P1, have been determined by X-ray analysis; they belong to the neoclerodane series. Isofruticolone has also been shown to belong to this series.

  X射线分析确定了19-乙酰基萘酚和另一种来自T. gnaphalodes的二萜类化合物的绝对构型，该构型可能与teucrin P 1相同。它们属于新环戊烷系列。异黄酮还被证明属于该系列。
• The Total Synthesis of Racemic Teucvin and 12-epi-Teucvin
  作者：Hsing-Jang Liu、Jia-Liang Zhu、I-Chia Chen、Renata Jankowska、Yongxin Han、Kak-Shan Shia

  DOI：10.1002/anie.200250681

  日期：2003.4.25
• Nakatsu, Tetsuo; Ito, Sho, Heterocycles, 1981, vol. 15, # 1, p. 241 - 244
  作者：Nakatsu, Tetsuo、Ito, Sho

  DOI：——

  日期：——
• Efficient Installation and Elaboration of C4-C6 fused Furan Moiety in the Total Synthesis of Teucrium Clerodane Diterpenoids
  作者：Jia-Liang Zhu、Hsing-Jang Liu、Yen-Ku Wu、I-Chia Chen

  DOI：10.3987/com-14-13045

  日期：——

  We previously reported the total synthesis of several Teucrium clerodane diterpenoids including teucvin (1), 12-epi-teucvin (2), montanin A (3) and teuscorolide (4) in a unified Diels-Alder approach. A full account for the tactical installation of the C4-C6 furan ring. of 3 from an alpha,beta-unsaturated lactone moiety, and the elaboration of the resulting furan unit into alpha,beta-unsaturated gamma-hydroxyl lactone for preparing 4 is discussed herein. In addition, the transformation of 3 and its 12-epimer into 1 and 2 by the air-mediated furan oxidation reaction is described.

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