紫杉宁 | 3835-52-7

• 物质功能分类: 天然产物 - 萜类
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 紫杉宁
• 英文名称: taxinine
• 英文别名: [(1R,2R,3R,5S,8R,9R,10R)-2,9,10-triacetyloxy-8,12,15,15-tetramethyl-4-methylidene-13-oxo-5-tricyclo[9.3.1.03,8]pentadec-11-enyl] (E)-3-phenylprop-2-enoate
• CAS: 3835-52-7
• 化学式: C₃₅H₄₂O₉
• 分子量: 606.713
• InChiKey: BAYHEZUZRPMUDM-RZHPVIQDSA-N

物化性质

• 熔点：
  264-265℃
• 比旋光度：
  D18 +137° (chloroform)
• 沸点：
  669.7±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  44
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  122
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  紫杉宁 在 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 四氧化锇 、 N-甲基吲哚酮 、 盐酸羟胺 、 四丁基氟化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 生成 2α-benzoyloxy-5β,20-epoxy-4α-hydroxy-9α,10β-isopropylidenedioxy-11-taxen-13-one
  参考文献：
  名称：

  Structure–activity relationships of some taxoids as multidrug resistance modulator

  摘要：

  1,7-Deoxy-4-deacetylbaccatin III (12) and its five analogues 6-9, 13, and their oxetane ring opened derivatives 14, 16, and 17, which were synthesized from taxinine, showed significant activity as MDR reversal agent by the assay of the calcein accumulation toward MDR human ovarian cancer 2780AD cells. The most effective compound 12 in this assay is actually efficient for the recovery of cytotoxic activity of paclitaxel (taxol), adriamycin (ADM), and vincristine (VCR) toward MDR 2780AD cells at the same level toward parental 2780 cells. This activity of 12 is very interesting because baccatin 111 (4) has no such MDR reversal activity but has cytotoxic activity. The essential functional groups inducing such a difference in biological activity between 4 and 12 are 4 alpha-acetoxyl for 4 and 4 alpha-hydroxyl for 12. In seven compounds possessing MDR reversal activity, compound 12 is the most desirable compound for anti-MDR cancer reversal agent, because it has the highest accumulation ability of anticancer agent in MDR cancer cells and weak cytotoxic activity. Compounds 8 and 13 showed significant cytotoxic activity toward HepG2 and VA-13, respectively, as well as MDR reversal activity. They are expected to become lead compounds for new types of anticancer agent or anti-MDR cancer agent. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2006.09.068

文献信息

• A 3,11-cyclotaxane from Taxus baccata
  作者：Giovanni Appendino、Patrizia Lusso、Pierluigi Gariboldi、Ezio Bombardelli、Bruno Gabetta

  DOI：10.1016/0031-9422(92)80455-n

  日期：1992.12

  Abstract A collection of yew needles afforded a taxane diester characterized by an additional bond between C-3 and C-11. The structure was elucidated by spectral methods, and further confirmed by synthesis from a known taxane derivative. A general procedure for the photocyclization of taxicins is reported.

  摘要 一组红豆杉针叶提供了一种紫杉烷二酯，其特征在于 C-3 和 C-11 之间的附加键。该结构通过光谱方法阐明，并通过由已知紫杉烷衍生物的合成进一步证实。报告了紫杉素光环化的一般程序。
• Syntheses of Taxuspine C Derivatives as Functional Inhibitors of P-Glycoprotein, an ATP-Associated Cell-Membrane Transporter.
  作者：Magoichi SAKO、Hikokazu SUZUKI、Kosaku HIROTA

  DOI：10.1248/cpb.46.1135

  日期：——

  UV-Irradiation of taxinine and related compounds in acetonitrile induced a smooth transannulation between the C-3 and C-11 positions without any influence from the C-2, C-9 and C-10 substituents to give tetracyclic taxuspine C derivatives in almost quantitative yields. Photochemical transannular reaction of taxoids possessing a cinnamoyl group in the side-chain was accompanied by an E,Z-isomerization

  在乙腈中紫外线照射紫杉碱及相关化合物可诱导C-3和C-11位置之间平稳过渡，而不受C-2，C-9和C-10取代基的影响，从而得到几乎定量的四环紫杉烷C衍生物产量。在侧链上具有肉桂酰基的紫杉烷类化合物的光化学跨环反应伴随着肉桂酰基部分的E，Z-异构化。发现长春新碱（一种对癌症化疗有用的药物）在具有多重耐药性的卵巢癌细胞中的细胞蓄积最有效地增加了5-O-苯甲酰化的5-O-癸氨酰紫杉醇C的含量。这表明5-O-苯甲酰化的红豆杉C衍生物可能是有前途的P糖蛋白功能抑制剂，它可作为癌症化疗药物的ATP相关外排泵。
• Stereoselective epoxidation of 4(20)-exomethylene in taxinine derivatives and assignment of the epoxide orientation by NMR
  作者：Hirokazu Hosoyama、Hideyuki Shigemori、Yasuko In、Toshimasa Ishida、Jun'ichi Kobayashi

  DOI：10.1016/s0040-4020(98)00018-0

  日期：1998.3

  Epoxidation of taxinine (1), taxinine A (2), and taxinine derivative 7 with m-chloroperbenzoic acid afforded the α-4(20)-epoxides selectively (α : β = 99 : 1), while epoxidation of taxinine derivatives 7 and 8 with dimethyldioxirane gave the β-4(20)-epoxides predominantly (α : β = 1 : 4∼5). The epoxide orientation was found to be assignable by magnitude of chemical shift differences between the geminal

  taxinine（环氧化1），taxinine A（2），和taxinine衍生物7与米，得到氯过苯甲酸的α-4（20） -环氧化物选择性（α：β = 99：1），而taxinine衍生物的环氧化7和8与二甲基二，得到β-4（20） -环氧化物主要（α：β = 1：4〜5）。发现环氧化物的取向可通过1 H NMR光谱中双环环氧质子之间的化学位移差异的大小来确定。1β-羟基浆果赤霉素I的相对立体化学（9通过X射线分析确定具有β-4（20）-环氧部分的），以提供环氧方向的有效分配。
• Facile Synthesis of a Novel Taxoid Closely Related to Bioactive Taxuspine D. Regio- and Stereo-Selective Hydration of Taxinine, a Naturally Occurring Taxane Diterpenoid.
  作者：Hikokazu SUZUKI、Magoichi SAKO、Kosaku HIROTA

  DOI：10.1248/cpb.46.857

  日期：——

  Treatment of taxinine, which is a taxane diterpenoid readily available from needles of the Japanese yew Taxus cuspidata, with a large excess amount of sodium borohydride in slightly hydrous N, N-dimethylformamide at ambient temperature resulted in regio- and stereo-selective hydration at the C11, C<12>-double bond to give an siomeric texuspine D derivative.

  在常温下，用大量过量的硼氢化钠在微水合的 N，N-二甲基甲酰胺中处理可从日本紫杉（Taxus cuspidata）针叶中获得的紫杉素二萜（taxane diterpenoid），结果在 C11、C<12>-双键处发生了区域和立体选择性水合反应，生成了一种西乌头蛇床子碱 D 衍生物。
• A taxane-11,12-oxide from Taxus yunnanensis
  作者：Qin Yue、Qi-Cheng Fang、Xiao-Tian Liang

  DOI：10.1016/0031-9422(96)00299-3

  日期：1996.10

  Abstract A new taxoid, decinnamoyl-taxinine B-11,12-oxide, was isolated from the leaves and stems of Taxus yunnanensis . This is the first example of an 11,12-epoxy taxoid isolated from the yew tree.

  摘要 从云南红豆杉的叶和茎中分离到了一种新的紫杉类，癸二酰紫杉碱B-11,12-氧化物。这是从紫杉树中分离出的 11,12-环氧紫杉醇的第一个例子。