7-triethylsilyl-13-dehydro-10-deacetylbaccatin III | 155588-21-9

• 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: 7-triethylsilyl-13-dehydro-10-deacetylbaccatin III
• 英文别名: 13-oxo-7-O-triethylsilyl-10-deacetylbaccatin III；10-deacetyl-13-deoxy-13-oxo-7-O-triethylsilylbaccatin III；[(1S,2S,3R,4S,7R,9S,10S,12R)-4-acetyloxy-1,12-dihydroxy-10,14,17,17-tetramethyl-11,15-dioxo-9-triethylsilyloxy-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-2-yl] benzoate
• CAS: 155588-21-9
• 化学式: C₃₅H₄₈O₁₀Si
• 分子量: 656.846
• InChiKey: IDVZOYNNJVXDHC-DMOTUGQFSA-N

物化性质

• 沸点：
  717.5±60.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  46
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.66
• 拓扑面积：
  146
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  7-triethylsilyl-13-dehydro-10-deacetylbaccatin III 在 吡啶 、 4-二甲氨基吡啶 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 环己烷 、 甲苯 为溶剂， 反应 22.5h， 生成 2-debenzoyl-7-(triethylsilyl)-13-oxobaccatin III
  参考文献：
  名称：

  紫杉醇的全合成。1. 逆合成、降解和重组

  摘要：

  已经开发了一种成功的策略，用于对映选择性合成紫杉醇 (1) 的天然立体异构体。该策略利用了来自环 A (10) 和 C (9) 的预制合成子的紫杉醇中央八元 B 环的会聚组装，随后引入了 D 环和侧链。降解研究证实了某些关键操作的可行性，包括 C13 位置的氧化 (35 3) 和区域选择性引入 C1-羟基、CZ苯甲酰氧基部分 (29 31)。此外，还开发了一种用于大规模生产 29（一种可用于 C2 模拟生产的衍生物）的便捷方法。

  DOI：

  10.1021/ja00107a006
• 作为产物：
  描述：

  10-脱乙酰基巴卡丁 III 在 吡啶 、 四丙基高钌酸铵 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 17.5h， 生成 7-triethylsilyl-13-dehydro-10-deacetylbaccatin III
  参考文献：
  名称：

  紫杉醇的全合成。1. 逆合成、降解和重组

  摘要：

  已经开发了一种成功的策略，用于对映选择性合成紫杉醇 (1) 的天然立体异构体。该策略利用了来自环 A (10) 和 C (9) 的预制合成子的紫杉醇中央八元 B 环的会聚组装，随后引入了 D 环和侧链。降解研究证实了某些关键操作的可行性，包括 C13 位置的氧化 (35 3) 和区域选择性引入 C1-羟基、CZ苯甲酰氧基部分 (29 31)。此外，还开发了一种用于大规模生产 29（一种可用于 C2 模拟生产的衍生物）的便捷方法。

  DOI：

  10.1021/ja00107a006

文献信息

• Novel chemistry of taxol. Retrosynthetic and synthetic studies
  作者：K. C. Nicolaou、P. G. Nantermet、H. Ueno、R. K. Guy

  DOI：10.1039/c39940000295

  日期：——

  10-Deacetyl baccatin III 2 was used in the synthesis of compounds 4–6 and 11–15, all of which were converted to Taxol 1via efficient synthetic pathways

  10-去乙酰基浆果赤霉素III在化合物4至6以及11至15的合成中被使用，这些化合物通过有效的合成途径最终转变为紫杉醇。
• Synthesis of modified baccatins via an oxidation-reduction protocol
  作者：Giovanni Appendino、Jasmin Jakupovic、Giancarlo Cravotto、Renata Enriù、Marcella Varese、Ezio Bombardelli

  DOI：10.1016/0040-4039(95)00451-h

  日期：1995.5

  (12R)-7-Trietylsilyl-11-dihydro-10-deacetylbaccatin III (2), 10-epi-10-deacetylbaccatin III (4) and the 7,8-seco baccatin III (5a) were synthesized from 10-deacetylbaccatin III via an oxidation-reduction protocol.

  (12R)-7-三乙基硅烷基-11-二氢-10-去乙酰基百咯碱III（2）、10-表-10-去乙酰基百咯碱III（4）和7,8-断裂百咯碱III（5a）是通过氧化还原协议从10-去乙酰基百咯碱III合成而来。
• A New Method to Modify the C-4 Position of 10-Deacetylbaccatin III.
  作者：Kouichi UOTO、Haruhiro TAKENOSHITA、Takashi ISHIYAMA、Hirofumi TERASAWA、Tsunehiko SOGA

  DOI：10.1248/cpb.45.2093

  日期：——

  We have developed a new method to modify the C-4 position of 10-deacetylbaccatin III (5) using the C-4 acetoxy anion of the 13-keto derivative (7) and various alkyl halides. The method developed herein shound be very useful for the preparation of C-4 modified taxoid analogs.

  我们开发了一种新方法，利用 13-酮衍生物 (7) 的 C-4 乙酰氧基阴离子和各种烷基卤化物对 10-脱乙酰基巴卡丁 III (5) 的 C-4 位置进行修饰。这种方法对于制备 C-4 修饰类紫杉醇类似物非常有用。
• Design, Synthesis and Structure−Activity Relationships of Novel Taxane-Based Multidrug Resistance Reversal Agents
  作者：Iwao Ojima、Christopher P. Borella、Xinyuan Wu、Pierre-Yves Bounaud、Cecilia Fumero Oderda、Matthew Sturm、Michael L. Miller、Subrata Chakravarty、Jin Chen、Qing Huang、Paula Pera、Tracy A. Brooks、Maria R. Baer、Ralph J. Bernacki

  DOI：10.1021/jm049483y

  日期：2005.3.1

  A series of novel taxane-based multidrug resistance (MDR) reversal agents (TRAs) has been designed and synthesized. Structure-activity relationship (SAR) study clearly indicates that modification of the C-7 position with hydrophobic arenecarbonyleinnamoyl groups brings about high potency against drug efflux mediated by P-glycoprotein (P-gp). Six TRAs exhibit ability to modulate a wide range of ATP-binding cassette (ABC) transporters, such as P-gp, multidrug resistance-associated protein 1 (MRP1), and breast cancer resistance protein (BCRP), which may serve as novel broad-spectrum modulators of ABC transporters.
• Structure–activity relationship study of taxoids for their ability to activate murine macrophages as well as inhibit the growth of macrophage-like cells
  作者：Iwao Ojima、Cecilia L Fumero-Oderda、Scott D Kuduk、Zhuping Ma、Fumiko Kirikae、Teruo Kirikae

  DOI：10.1016/s0968-0896(03)00181-0

  日期：2003.7

  A series of new taxoids modified at the C-3', C-3'N, C-10, C-2 and C-7 positions has been designed, synthesized and evaluated for their potency to induce NO and TNF production by peritoneal murine macrophages (Mphi) from LPS-responsive C3H/HeN and LPS-hyporesponsive C3H/HeJ strains and human blood cells, and for their ability to inhibit the growth of Mphi-like cell lines J774.1 and J7.DEF3. The SAR-study has shown that the nature of the substituents at these positions have critical effect on the induction of TNF and NO production by Mphi. Positions G-3' and C-10 are the most flexible and an intriguing effect of the length of the substituents at the C-10 position is observed for taxoids bearing a straight chain alkanoyl moiety. An aromatic group at the C-3'N and C-2 positions is required for the activity, while only hydroxyl or acetyl substituents seem to be tolerated at the C-7 position. The natural stereochemistry in the C-13 isoserine side chain of the taxoids is an absolute requirement for macrophage activation. It has also been clearly shown that there is no correlation between the ability of the taxoids to induce TNF/NO production in C3H/HeN M and the cytotoxicity against Mphi-like cells. (C) 2003 Elsevier Science Ltd. All rights reserved.