24,32-双-O-(tert-butyldimethylsilyl)-他克莫司 | 133941-75-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯内酰胺
• 中文名称: 24,32-双-O-(tert-butyldimethylsilyl)-他克莫司
• 英文名称: 24,33-Bis-(t.butyl-dimethylsilyl)-FK 506
• 英文别名: 24,33-bis-OTBDMS-FK506；24,32-Bis-O-(tert-butyldimethylsilyl)-FK-506；(1R,9S,12S,13S,14S,17R,18E,21S,23S,24R,25S,27R)-14-[tert-butyl(dimethyl)silyl]oxy-12-[(E)-1-[(1R,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxycyclohexyl]prop-1-en-2-yl]-1-hydroxy-23,25-dimethoxy-13,19,21,27-tetramethyl-17-prop-2-enyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetrone
• CAS: 133941-75-0
• 化学式: C₅₆H₉₇NO₁₂Si₂
• 分子量: 1032.56
• InChiKey: ZMQPVYFWZQHALN-SWHZMJOBSA-N

物化性质

• 熔点：
  >72° (dec.)
• 沸点：
  899.3±75.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿（微溶）、乙酸乙酯（微溶）

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  71
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  156
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  24,32-双-O-(tert-butyldimethylsilyl)-他克莫司 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 2.5h， 生成 他克莫司
  参考文献：
  名称：

  Regio- and stereoselective preparation of ascomycin-d1 and FK 506-d1

  摘要：

  免疫抑制大环内酯药物阿斯科霉素1和FK 506 2在C(32)处采用Curran的自由基转位方法进行立体选择性氘代化。测试了AIBN和Et3B/O2作为自由基引发剂，用Bu3SnD作为还原剂进行自由基转位/还原步骤。尽管仅有细微结构差异，阿斯科霉素和FK 506在自由基转位/还原条件下表现出显著不同的行为。使用Et3B/O2作为引发剂时观察到更高的立体选择性，推测是由于在这种情况下反应温度较低。© 2002 John Wiley & Sons, Ltd.

  DOI：

  10.1002/jlcr.558
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 他克莫司 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以95%的产率得到24,32-双-O-(tert-butyldimethylsilyl)-他克莫司
  参考文献：
  名称：

  Storable Arylpalladium(II) Reagents for Alkene Labeling in Aqueous Media

  摘要：

  We show that arylpalladium(II) reagents linked to biotin and indocyanine dye residues can be prepared by decarboxylative palladation of appropriately substituted electron-rich benzoic acid derivatives. When prepared under the conditions described, these organometallic intermediates are tolerant of air and water, can be stored for several months in solution in dimethyl sulfoxide, and permit biotin- and indocyanine dye-labeling of functionally complex olefinic substrates in water by Heck-type coupling reactions.

  DOI：

  10.1021/ja206339s

文献信息

• Highly selective reactions of FK506 with diazomethane
  作者：A.J.F. Edmunds、K. Baumann、M. Grassberger、G. Schulz

  DOI：10.1016/0040-4039(91)85034-3

  日期：1991.11

  Three modes of diazomethane reactivity, namely oxirane formation, O-methylation and cyclopropanation, can be accomplished with excellent selectivity on the multifunctional molecule FK506.

  重氮甲烷反应性的三种模式，即环氧乙烷形成，O-甲基化和环丙烷化，可以在多功能分子FK506上以优异的选择性完成。
• Rapid synthesis of 11C-labeled FK506 for positron emission tomography
  作者：Yoshihiro Murakami、Akio Kuroda、Kazuhiko Osoda、Shintaro Nishimura

  DOI：10.1016/s0040-4039(02)02705-3

  日期：2003.1

  The present study describes a rapid synthesis method for labeled [C-11]FK506 for positron emission tomography (PET). A one-pot reaction from [C-11]CH3I, involving a Wittig reaction as the key carbon-carbon bond formation was developed. The chemical process was accomplished using a designed, fully automated synthetic apparatus, and an injectable solution of [C-11]FK506 was obtained in only 34 min from [C-11]CH3I. The decay-corrected radiochemical yield based on [C-11]CH3I was 11.9%, and the specific activity was 39.8 GBq/mumol. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Synthesis of derivatives of FK 506 and FR 900520: modifications at the binding domain
  作者：Gerhard Emmer、Sabine Weber-Roth

  DOI：10.1016/s0040-4020(01)90178-4

  日期：1992.7

  The synthesis of 9-deoxo-FK 506 (13a), 9-deoxo-FR 900520 (13b), 9-deoxo-10(R)-deoxy-FR 900520 (14) and its 10(S) isomer 15 is described. Radical deoxygenation/elemination of the 9-di-hydro-9,10-thiocarbonates 5a,5b,6a and 6b gave the 9,10 unsaturated compounds 7a (7b) or 8a (8b) which were further transferred by hydration or hydrogenation. Different E/Z ratios of 7a (7b) were obtainted when nBu3SnH or [(CH3)3Si]3SiH in combination with AIBN or Et3B were used, allowing the selective preparation of both isomers. Two possible reaction mechanisms are discussed.
• Regio- and stereoselective preparation of ascomycin-d1 and FK 506-d1
  作者：Murat Acemoglu、Hendrik Andres、Thomas Moenius

  DOI：10.1002/jlcr.558

  日期：2002.4

  The immunosuppressive macrolides ascomycin 1 and FK 506 2 were stereoselectively deuteriated at C(32) using Curran's radical translocating method. Both AIBN and Et3B/O2 were tested as radical initiator for the radical translocation/reduction step with Bu3SnD as reducing agent. Despite only minor structural differences, ascomycin and FK 506 showed remarkably different behaviour under the radical translocation/reduction conditions. Higher stereoselectivities were observed with Et3B/O2 as initiator, presumably due to lower reaction temperatures applied in this case. Copyright © 2002 John Wiley & Sons, Ltd.

  免疫抑制大环内酯药物阿斯科霉素1和FK 506 2在C(32)处采用Curran的自由基转位方法进行立体选择性氘代化。测试了AIBN和Et3B/O2作为自由基引发剂，用Bu3SnD作为还原剂进行自由基转位/还原步骤。尽管仅有细微结构差异，阿斯科霉素和FK 506在自由基转位/还原条件下表现出显著不同的行为。使用Et3B/O2作为引发剂时观察到更高的立体选择性，推测是由于在这种情况下反应温度较低。© 2002 John Wiley & Sons, Ltd.
• Storable Arylpalladium(II) Reagents for Alkene Labeling in Aqueous Media
  作者：Rebecca L. Simmons、Robert T. Yu、Andrew G. Myers

  DOI：10.1021/ja206339s

  日期：2011.10.12

  We show that arylpalladium(II) reagents linked to biotin and indocyanine dye residues can be prepared by decarboxylative palladation of appropriately substituted electron-rich benzoic acid derivatives. When prepared under the conditions described, these organometallic intermediates are tolerant of air and water, can be stored for several months in solution in dimethyl sulfoxide, and permit biotin- and indocyanine dye-labeling of functionally complex olefinic substrates in water by Heck-type coupling reactions.