10-desacetoxybaccatin | 150930-84-0

• 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: 10-desacetoxybaccatin
• 英文别名: 10-Deoxybaccatin；[(1S,2S,3R,4S,7R,9S,10S,15S)-4-acetyloxy-1,9,15-trihydroxy-10,14,17,17-tetramethyl-11-oxo-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-2-yl] benzoate
• CAS: 150930-84-0
• 化学式: C₂₉H₃₆O₉
• 分子量: 528.599
• InChiKey: AFGPDNSRDMIDIC-HDSNEEJHSA-N

物化性质

• 熔点：
  230-232 °C(Solv: chloroform (67-66-3); hexane (110-54-3))
• 沸点：
  678.7±55.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  140
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  10-desacetoxybaccatin 在 三乙基氯硅烷 、 碳酸氢钠 作用下， 以 吡啶 、 水 、 乙酸乙酯 为溶剂， 反应 48.0h， 以91%的产率得到10-Deacetoxy-7-(triethylsilyl)baccatin III
  参考文献：
  名称：

  Process for the preparation of baccatin III analogs bearing new C2 and C4 functional groups

  摘要：

  这段文字是关于制备紫杉醇前体化合物——特别是baccatin III或10-desacetyl baccatin III的衍生物或类似物——的化学工艺描述。该工艺涉及对baccatin III或10-desacetyl baccatin III的C2位置上的苯甲酸酯基团和/或C4位置上的醋酸酯基团进行选择性还原，将它们转化为相应的羟基，并进一步转化为R7COO—和/或R8COO—，其中R7和R8独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C8炔基、单环芳基或单环杂芳基。以下是中文翻译： 制备baccatin III或10-去乙酰基baccatin III的衍生物或类似物的工艺，该衍生物或类似物具有除苯甲酸酯以外的C2取代基和/或除醋酸酯以外的C4取代基，其中baccatin III或10-去乙酰基baccatin III衍生物的C2位苯甲酸酯取代基和/或C4位醋酸酯取代基被选择性地还原为相应的羟基，并且分别转化为R7COO—和/或R8COO—，其中R7和R8独立地为H，C1-C6烷基，C2-C6烯基，C2-C8炔基，单环芳基或单环杂芳基。

  公开号：

  US06727369B1
• 作为产物：
  描述：

  10-脱乙酰基巴卡丁 III 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.1h， 生成 10-desacetoxybaccatin
  参考文献：
  名称：

  浆果赤霉素Ⅲ衍生物对SaⅡ试剂的反应性

  摘要：

  在各种质子供体存在下10-去乙酰基浆果赤霉素III（1）对sa II试剂的反应性研究导致9β-二氢-10-去乙酰基浆果赤霉素III（7）和2-debenzoyl-9β-dihydro-10的有效合成。-脱乙酰基浆果赤霉素III（9）。

  DOI：

  10.1016/0040-4039(95)00100-q

文献信息

• The chemistry of the taxane diterpene: Stereoselective synthesis of 10-deacetoxy-11,12-epoxypaclitaxel
  作者：Geraldine C.B. Harriman、Ravi K. Jalluri、Gary L. Granewald、David G. Vander Velde、Gunda I. Georg、Richard H. Himes

  DOI：10.1016/0040-4039(95)01928-b

  日期：1995.12

  10-deacetoxypaclitaxel (9) was accomplished with meta-chloroperbenzoic acid leading to a novel pentacyclic ring system. Hydroxyl directed delivery of the epoxidizing agent did not appear to play a role in the stereoselectivity of the reaction as epoxidation occurred at the β-face of the molecule. 10-Deacetoxy-11,12-epoxypaclitaxel (10) proved to be more active than paclitaxel (1) in the microtubule assembly assay and

  用间氯过苯甲酸完成10-deacetoxybaccatin III（6）和10-deacetoxypaclitaxel（9）中烯烃的环氧化反应，产生了新的五环体系。由于在分子的β-面发生环氧化，因此环氧直接引导的环氧化剂似乎没有在反应的立体选择性中起作用。在微管组装试验中，10 -Deacetoxy-11,12-epoxypaclitaxel（10）比紫杉醇（1）更具活性，对紫杉醇对B16黑色素瘤细胞的毒性比紫杉醇低三倍。
• Process for the preparation of 10-desacetoxybaccatin III
  申请人：Florida State University

  公开号：US05654447A1

  公开（公告）日：1997-08-05

  A process for abstracting a C10 hydroxy, acyloxy or sulfonyloxy substituent from a taxane in which the C10 hydroxy, acyloxy or sulfonyloxy substituted taxane is reacted with samarium diiodide.

  一种从紫杉烷中提取C10羟基、酰氧基或磺酰氧基取代基的过程，其中将C10羟基、酰氧基或磺酰氧基取代的紫杉烷与二碘化钐反应。
• 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.
• Stereoselective synthesis of 9β-hydroxytaxanes via reduction with samarium diiodide
  作者：Gunda I. Georg、Zacharia S. Cheruvallath、David G. Vander Velde、Richard H. Himes

  DOI：10.1016/0040-4039(95)00142-y

  日期：1995.3

  Reaction of baccatin III and paclitaxel with samarium diiodide yielded the corresponding l0-deacetyl-9 beta-hydroxy derivatives. When 10-deacetylbaccatin III and docetaxel were subjected to the same reaction conditions the corresponding 9 beta-hydroxy and 10-dehydroxy-9 beta-hydroxy analogues were isolated.
• The Chemistry of the Taxane Diterpene:  Stereoselective Reductions of Taxanes
  作者：Gunda I. Georg、Geraldine C. B. Harriman、Apurba Datta、Syed Ali、Zacharia Cheruvallath、Dinah Dutta、David G. Vander Velde、Richard H. Himes

  DOI：10.1021/jo981194s

  日期：1998.11.1

  Stereoselective reductions of taxanes are detailed. Chelation-controlled reductions employing SmI2 are described for the stereoselective reduction of the 9-keto functionality of the diterpene moiety of several taxanes. In all cases the 9 beta-hydroxy stereochemistry was obtained exclusively. In addition to C9 reduction, partial C10-deoxygenation via beta-elimination was observed. Lower reaction temperatures favored the reduction pathway without beta-elimination. Acetic acid as the proton source gave higher yields and cleaner reaction products. This chemistry provided access to taxanes with 9 beta-hydroxy, 10 beta-hydroxy stereochemistry. Evidence is presented, suggesting that chelation of samarium with the 7 beta-hydroxyl group is required for the reduction of the C9 ketone moiety. The synthesis of paclitaxel analogues, possessing the 9 alpha-hydroxy, 10 alpha-hydroxy stereochemistry was also achieved. Reduction of the 10-ketone group of 10-oxopaclitaxel employing NaBH4 produced 10-deacetyl-10-epipaclitaxel stereoselectively. Using an excess of NaBH4 in this reaction gave exclusively the 9 alpha-hydroxy, 10 alpha-hydroxy paclitaxel analogue.