2-Debenzoyl-7,13-bis(triethylsilyl)baccatin III | 150542-00-0

• 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
• 英文名称: 2-Debenzoyl-7,13-bis(triethylsilyl)baccatin III
• 英文别名: 2-O-debenzoyl-7,13-di-O-TES-baccatin III；[(1S,2S,3R,4S,7R,9S,10S,12R,15S)-4-acetyloxy-1,2-dihydroxy-10,14,17,17-tetramethyl-11-oxo-9,15-bis(triethylsilyloxy)-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-12-yl] acetate
• CAS: 150542-00-0
• 化学式: C₃₆H₆₂O₁₀Si₂
• 分子量: 711.053
• InChiKey: BHFRZAKOAUMLBR-NDPOWFEBSA-N

物化性质

• 沸点：
  662.5±55.0 °C(predicted)
• 密度：
  1.13±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.85
• 重原子数：
  48
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  138
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2-Debenzoyl-7,13-bis(triethylsilyl)baccatin III 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 氢氟酸 、 N,N'-二环己基碳二亚胺 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 生成 2-debenzoyl-2-acetyl-7-triethylsilylbaccatin III
  参考文献：
  名称：

  摘要：

  Crystals of the C2-acetate analog of paclitaxel, grown from a mixture of isopropyl alcohol and methanol, belong to the space group P2(1) with a = 9.058(3), b = 18.306(5), c = 15.043(1) Angstrom, beta 97.09(1)degrees, Z = 2, V = 2475.1(9)Angstrom(3), D-calc = 1.269 gcm(-3) and mu = 0.75 cm(-1). The structure was determined by direct methods and refined to R(F) = 0.054 and wR(F) = 0.057 for 605 variables and 3496 observed reflections. The paclitaxel side chain possesses a conformation similar to that observed in the crystal structure of docetaxel (Taxotere(R)). A three dimensional network of hydrogen bonds is formed through solvent molecules and stabilizes the crystal lattice.

  DOI：

  10.1023/a:1016236014766
• 作为产物：
  描述：

  巴卡丁 III 在 咪唑 、 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 2-Debenzoyl-7,13-bis(triethylsilyl)baccatin III
  参考文献：
  名称：

  紫杉醇构效关系：2-脱氧紫杉醇的合成及生物学评价

  摘要：

  从浆果赤霉素III中分九步制备2-脱氧紫杉醇2。合成的关键步骤是C-2处的Barton型脱氧。发现该化合物相对于紫杉醇具有大大降低的抗肿瘤活性。

  DOI：

  10.1016/s0040-4039(00)73661-6

文献信息

• New and Effective Synthesis of 7-Triethylsilylbaccatin III from 7<i>β</i>,13<i>α</i>-Bistriethylsiloxy-1<i>β</i>,2<i>α</i>,10<i>β</i>-trihydroxy-9-oxo-4(20),11-taxadiene
  作者：Isamu Shiina、Masahiro Saitoh、Koji Nishimura、Katsuyuki Saitoh、Teruaki Mukaiyama

  DOI：10.1246/cl.1996.223

  日期：1996.3

  7β,13α-Bistriethylsiloxy-1β,2α,10β-trihydroxy-9-oxo-4(20),11-taxadiene (2), derived from 10-deacetylbaccatin III via degradation of oxetane ring, was conveniently converted into 7-triethylsilylbaccatin III (1) by way of a new and effective method for constructing oxetane ring. Thus, the synthesis of a precursor of taxol from novel taxoid 2 was accomplished.

  7β,13α-双三乙基硅氧基-1β,2α,10β-三羟基-9-氧代-4(20),11-紫杉二烯（2）是由 10-脱乙酰基巴卡丁 III 通过氧杂环降解得到的，通过一种新的、有效的氧杂环构建方法，可方便地将其转化为 7-三乙基硅基巴卡丁 III（1）。这样，就完成了从新型类固醇 2 合成紫杉醇前体的过程。
• Facile AB ring cleavage reactions of taxoids
  作者：Mahendra D. Chordia、Milind M. Gharpure、David G.I. Kingston

  DOI：10.1016/0040-4020(95)00823-q

  日期：1995.11

  Two facile B ring cleavage reactions of taxoids related to paclitaxel are reported. Treatment of a 13-chlorobaccatin with azide ion led to cleavage of the C-10/C-11 bond and formation of a hemiketal product. Treatment of a protected 2-debenzoyl paclitaxel with MnO2 yielded a ketoaldehyde in which the C-1/C-2 bond had been cleaved and the side chain had been eliminated.

  据报道与紫杉醇有关的类紫杉醇的两个容易的B环裂解反应。用叠氮化物离子处理13-氯浆果赤霉素导致C-10 / C-11键的断裂和半缩醛产物的形成。用MnO 2处理受保护的2-脱苯甲酰基紫杉醇得到酮醛，其中C-1 / C-2键已断裂并且侧链已被消除。
• The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates
  作者：Shu-Hui Chen、Stella Huang、Qi Gao、Jerzy Golik、Vittorio Farina

  DOI：10.1021/jo00085a040

  日期：1994.3

  In the course of a synthetic program aimed at systematic defunctionalization of the taxol core for structure activity studies, a number of radical-based deoxygenation reactions were carried out on baccatin III derivatives. In this connection, we have discovered that formation of radicals at positions C-1, C-2, and C-7 in the taxane core of baccatin III results in a number of skeletal rearrangement cascades. Furthermore, the exact composition of the product mixture depends on the specific tin (or silicon) hydride used for the reduction. In the case of C-2- and C-7-derived radicals, direct quenching with tin hydrides without rearrangement was possible under some conditions. However, we were unable to find conditions to quench the C-1 radical, since rearrangement pathways always predominate in this case.
• Conformationally restricted paclitaxel analogues: Macrocyclic mimics of the “hydrophobic collapse” conformation
  作者：Thomas C. Boge、Zhi-Jun Wu、Richard H. Himes、David G. Vander Velde、Gunda I. Georg

  DOI：10.1016/s0960-894x(99)00522-3

  日期：1999.10

  Conformationally restricted macrocyclic analogues of paclitaxel were prepared, by connecting the 3'-phenyl group and the 2-benzoate moiety with two-atom tethers to mimic the "hydrophobic collapse" paclitaxel conformation. The analogues did not show activity in a tubulin assembly assay. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Studies on the photochemistry of taxol®
  作者：Shi-Hui Chen、Vittorio Farina、Stella Huang、Qi Gao、Jerzy Golik、Terrence W. Doyle

  DOI：10.1016/s0040-4020(01)85337-0

  日期：1994.1

  Irradiation of taxol at 280 nm in a Rayonet reactor yielded a novel pentacyclic derivative containing a new bond between C-3 and C-II. The proposed mechanism involves a triplet intermediate and the first event of the oxa-di-pi-merhane rearrangement. Taxane derivatives that lack both the benzoate at C-2 and the benzamide function at C-3' do not undergo the rearrangement, suggesting the intervention of an intramolecular energy transfer. Irradiation at 300 nm also effects extrusion of the C-9 carbonyl, yielding a ring-contracted product.