Acetic acid (4aS,6aR,7S,7aR,10aR,10bS,10cR)-10a-hydroxy-3,3,6a,9,9-pentamethyl-10-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-4a,6a,7,7a,8,9,10,10a,10b,10c-decahydro-1H-2,4-dioxa-pentaleno[1,2-a]naphthalen-7-yl ester | 220487-50-3

• 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: Acetic acid (4aS,6aR,7S,7aR,10aR,10bS,10cR)-10a-hydroxy-3,3,6a,9,9-pentamethyl-10-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-4a,6a,7,7a,8,9,10,10a,10b,10c-decahydro-1H-2,4-dioxa-pentaleno[1,2-a]naphthalen-7-yl ester
• 英文别名: [(1S,2R,7S,10R,11S,12R,15Z,16R)-16-hydroxy-5,5,10,14,14-pentamethyl-15-[2-(2-methyl-1,3-dioxolan-2-yl)ethylidene]-4,6-dioxatetracyclo[8.6.0.02,7.012,16]hexadec-8-en-11-yl] acetate
• CAS: 220487-50-3
• 化学式: C₂₇H₄₀O₇
• 分子量: 476.61
• InChiKey: AJIRHGZENVYBHA-JTSQSROQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Acetic acid (4aS,6aR,7S,7aR,10aR,10bS,10cR)-10a-hydroxy-3,3,6a,9,9-pentamethyl-10-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-4a,6a,7,7a,8,9,10,10a,10b,10c-decahydro-1H-2,4-dioxa-pentaleno[1,2-a]naphthalen-7-yl ester 在 镍 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium hydroxide 、 bis(acetylacetonate)oxovanadium 、 potassium tert-butylate 、 氢气 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 癸烷 、 水 、 苯 为溶剂， 反应 0.33h， 生成 (1S,2R,3'R,7S,10S,11E,15R)-5,5,10,14,14-pentamethyl-3'-[(2-methyl-1,3-dioxolan-2-yl)methyl]spiro[4,6-dioxatricyclo[8.6.0.02,7]hexadec-11-ene-15,2'-oxirane]-16-one
  参考文献：
  名称：

  Studies towards the total synthesis of taxoids The aldol-annelation-fragmentation strategy

  摘要：

  We describe an aldol-annelation-fragmentation strategy culminating in the stereoselective synthesis of the whole 20-carbon A-seco taxane framework 1 in only 12 linear steps starting from the two achiral aldol partners 2 and 3. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10703-1
• 作为产物：
  描述：

  Acetic acid (3aR,3bS,4R,7aR,8S,8aR)-4-hydroxymethyl-2,2,7a-trimethyl-3-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-5-oxo-3a-trimethylsilanyloxy-1,2,3,3a,3b,4,5,7a,8,8a-decahydro-cyclopenta[a]inden-8-yl ester 在 sodium tetrahydroborate 、 cerium(III) chloride 、 2,2-DMP 、 四丁基氟化铵 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 7.33h， 生成 Acetic acid (4aS,6aR,7S,7aR,10aR,10bS,10cR)-10a-hydroxy-3,3,6a,9,9-pentamethyl-10-[2-(2-methyl-[1,3]dioxolan-2-yl)-eth-(Z)-ylidene]-4a,6a,7,7a,8,9,10,10a,10b,10c-decahydro-1H-2,4-dioxa-pentaleno[1,2-a]naphthalen-7-yl ester
  参考文献：
  名称：

  Studies towards the total synthesis of taxoids The aldol-annelation-fragmentation strategy

  摘要：

  We describe an aldol-annelation-fragmentation strategy culminating in the stereoselective synthesis of the whole 20-carbon A-seco taxane framework 1 in only 12 linear steps starting from the two achiral aldol partners 2 and 3. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10703-1

文献信息

• Stereoselective Construction of a Highly Functionalized Taxoid ABC-Ring System: the C2-C9 Oxa-Bridge Approach
  作者：Sylvain Hamon、Nicolas Birlirakis、Loïc Toupet、Siméon Arseniyadis

  DOI：10.1002/ejoc.200500347

  日期：2005.10

  and hence no need for chromatographic separation. A temporary oxa-bridge (C2/C9) was used as a problem-solving approach. The key step in the planned sequence was based on achieving the last C–C bonding between C11 and C12, following a successful C11 functionalization. X-ray analyses of 8b, 17, 18, 19, 20, and 21, together with extensive use of 800 MHz 1H (200 MHz 13C) NMR spectra, support the suggested

  本研究的目标是通过本实验室开发的三反应序列组装具有高水平立体控制的紫杉素二萜骨架的 20 碳单元 1。该策略涉及七个 C-C 键形成操作以及 18 个官能团转换，完全规避了立体选择性问题。此外，没有异构体形成，因此不需要色谱分离。临时 oxa 桥 (C2/C9) 被用作解决问题的方法。计划序列中的关键步骤是基于在成功的 C11 功能化之后实现 C11 和 C12 之间的最后一个 C-C 键合。8b、17、18、19、20 和 21 的 X 射线分析，以及 800 MHz 1H (200 MHz 13C) NMR 光谱的广泛使用，支持建议的结构。(© Wiley-VCH Verlag GmbH &
• Studies towards the total synthesis of taxoids: a rapid entry into bicyclo[6.4.0]dodecane ring system. Part 1
  作者：Siméon Arseniyadis、Marı́a del Rosario Rico Ferreira、José Quı́lez del Moral、José Ignacio Martı́n Hernando、Pierre Potier、Loı̈c Toupet

  DOI：10.1016/s0957-4166(98)00434-0

  日期：1998.11

  We report a short and stereocontrolled synthesis of the taxoid BC-subunit (+)-5 embodying the whole carbon framework and most of the required oxygen functionalities for further elaboration. Enantiomeric purity was secured at an early stage by resolution involving derivatization with (S)-2-acetoxypropionyl chloride on (+/-)-10b. (C) 1998 Elsevier Science Ltd. All rights reserved.
• The aldol–annulation–fragmentation strategy toward the taxoid diterpene framework revisited. Instructive failures in the chemistry of medium ring containing systems
  作者：Sylvain Hamon、María del Rosario Rico Ferreira、José Quílez del Moral、José I. Martín Hernando、José I. Candela Lena、Nicolas Birlirakis、Loı¨c Toupet、Siméon Arseniyadis

  DOI：10.1016/j.tetasy.2005.08.044

  日期：2005.10

  Central intermediate 5 for the taxoid diterpene framework, prepared by the aldol-annulation sequence, permitted the construction of A-secotaxane frameworks incorporating differentiatable olefin and oxygen functionalities suitable for further elaboration. The key BC-subunits 9 and 8 have proven amenable to efficient conversion into both oxa-bridged 7 and its central eight-membered B-ring analogue 6, providing two potential precursors for taxoid construction. Although their further elaboration into 4 was not progressed at this stage.. 6 and 7 are potentially useful synthetic intermediates. Extensive structural studies that included 800 MHz (1)H (200 MHz (13)C) NMR as well as X-ray crystallographic analyses of 7, 17, and 20 have contributed to the unambiguous elucidation of all the complex structures synthesized. (c) 2005 Elsevier Ltd. All rights reserved.
• Arseniyadis, Simeon; Alves, Rosemeire Brondi; De Freitas, Rossimiriam Pereira, Heterocycles, <hi>1997</hi>, vol. 46, # 1, p. 727 - 764
  作者：Arseniyadis, Simeon、Alves, Rosemeire Brondi、De Freitas, Rossimiriam Pereira、Dorado, Manuel Munoz、Yashunsky, Dmitry V.、Potier, Pierre、Toupet, Loic

  DOI：——

  日期：——