2-((1S,6S)-1,3,7,7-tetramethylbicyclo[4.4.0]dec-2-en-2-yl)ethyl acetate | 61047-04-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-((1S,6S)-1,3,7,7-tetramethylbicyclo[4.4.0]dec-2-en-2-yl)ethyl acetate
• 英文别名: 12-acetoxy-13,14,15,16-tetranorlabd-8-ene；12-acetoxy-Δ^8,9-bicyclohomofarnesen-12-ol；2-[(4aS,8aS)-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydronaphthalen-1-yl]ethyl acetate
• CAS: 61047-04-9
• 化学式: C₁₈H₃₀O₂
• 分子量: 278.435
• InChiKey: IXUDSASFSGZWEN-FUHWJXTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-((1S,6S)-1,3,7,7-tetramethylbicyclo[4.4.0]dec-2-en-2-yl)ethyl acetate 在 吡啶 、 间氯过氧苯甲酸 、 tris-(4-bromophenyl)aminium hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (5S,8R,10S)-9-(2-acetoxyethyl)-austrodor-9-one
  参考文献：
  名称：

  Synthesis and absolute stereochemistry of marine nor-sesquiterpene austrodoric acid

  摘要：

  An enantiospecific synthesis of the nor-sesquiterpene austrodoric acid 1, recently isolated from an Antarctic marine mollusk, has been achieved. The synthetic strategy was based on the ring contraction of a suitable homo-drimanic epoxide,3, easily obtained from commercial (+)-sclareolide 4. The absolute configuration of natural austrodoric acid, not determined previously, has been now established by analyzing the CD profile of synthetic 1, which was the same as the natural compound. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.10.024
• 作为产物：
  描述：

  反式,反式-金合欢醇 在 copper(l) iodide 双氧水 、 三溴化磷 、 mercuric triflate 、 sodium carbonate 、 N,N-二甲基苯胺 作用下， 以 吡啶 、 硝基甲烷 为溶剂， 反应 6.17h， 生成 2-((1S,6S)-1,3,7,7-tetramethylbicyclo[4.4.0]dec-2-en-2-yl)ethyl acetate
  参考文献：
  名称：

  Total synthesis and morphogenesis-inducing activity of (±)-thallusin and its analogues

  摘要：

  Total synthesis of (+/-)-thallusin was achieved using Hg(OTf)(2)-PhNMe2-induced olefin cyclization, and Suzuki coupling with a pyridyllboronic acid derivative. Hg(OTf)(2) also acted as a catalyst to isomerize the double bond into the more thermodynamically stable isomer when treated in toluene. Synthetic (+/-)-thallusin as well as an analogue showed morphogenesis-inducing activity. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.04.075

文献信息

• Scalable and sustainable electrochemical allylic C–H oxidation
  作者：Evan J. Horn、Brandon R. Rosen、Yong Chen、Jiaze Tang、Ke Chen、Martin D. Eastgate、Phil S. Baran

  DOI：10.1038/nature17431

  日期：2016.5.5

  transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications

  C-H 键直接功能化的新方法和策略开始重塑逆合成分析领域，影响天然产物、药物和材料的合成。由于烯酮和烯丙醇作为多功能中间体的实用性，以及它们在天然和非天然材料中的普遍性，烯丙基系统的氧化在这方面发挥了重要作用，可能是应用最广泛的 C-H 官能化。烯丙基氧化在数百种合成中具有特色，包括一些被视为“经典”的天然产物合成。尽管多次尝试提高这种转换的效率和实用性，大多数条件仍然使用剧毒试剂（基于有毒元素，如铬或硒）或昂贵的催化剂（如钯或铑）。这些要求在工业环境中是有问题的；目前，不存在可扩展和可持续的烯丙基氧化解决方案。因此，这种氧化策略很少用于大规模合成应用，限制了工业科学家采用这种逆合成策略。在这里，我们描述了一种电化学 C-H 氧化策略，它具有广泛的底物范围、操作简单性和高化学选择性。它使用廉价且容易获得的材料，并代表可扩展的烯丙基 C-H 氧化（以 100 克为单位证明），
• The first total synthesis and determination of the absolute configuration of chapecoderin A, B and C
  作者：Hisahiro Hagiwara、Fumihide Takeuchi、Masato Nozawa、Takashi Hoshi、Toshio Suzuki

  DOI：10.1016/j.tet.2004.01.004

  日期：2004.2

  The seco- and rearranged-labdanes, chapecoderins A 1, B 2, and C 3 have been synthesized for the first time starting from (S)-(+)-Wieland-Miescher ketone analogue 11. Their absolute configurations have been determined as depicted in the structures 1, 2 and 3.

  的开环-和重排-labdanes，chapecoderins阿1，B 2和C 3被合成首次从（起始小号） - （+） -维兰德-米舍尔酮类似物11。如所描绘的结构的绝对构型已经被确定1，2和3。
• First total synthesis of chapecoderin A: absolute configuration of the natural product
  作者：Hisahiro Hagiwara、Fumihide Takeuchi、Takashi Hoshi、Toshio Suzuki、Masayoshi Ando

  DOI：10.1016/s0040-4039(01)01647-1

  日期：2001.10

  A seco-labdane, chapecoderin A 1, has been synthesized starting from (S)-(+)-Wieland–Miescher ketone analogue 9. The absolute configuration has been determined to be 5S,10S.

  甲开环-labdane，chapecoderin阿1，已经合成从（起始小号） - （+） -维兰德-米舍尔酮类似物9。绝对构型已被确定为5小号，10小号。
• Enantioselective synthesis of 11-homodrim-7-en-9α,12,13-triol
  作者：P. F. Vlad、K. G. Edu、M. N. Koltsa、A. G. Chokyrlan、A. Nikolescu、K. Delyanu

  DOI：10.1007/s10600-011-9998-x

  日期：2011.9

  The enantioselective synthesis of 11-homodrim-7-en-9α,12,13-triol, a convenient synthon for preparing polyfunctional 11-homodrimane sesquiterpenoids, was carried out starting from norambreinolide, a cleavage product available from several bicyclic labdane diterpenoids.

  11-homodrim-7-en-9α,12,13-triol 是一种用于制备多官能团 11-homodrimane 倍半萜的简便合成物。
• Diastereoselective routes towards the austrodorane skeleton based on pinacol rearrangement: synthesis of (+)-austrodoral and (+)-austrodoric acid
  作者：Enrique Alvarez-Manzaneda、Rachid Chahboun、Inmaculada Barranco、Eduardo Cabrera、Esteban Alvarez、Armando Lara、Ramón Alvarez-Manzaneda、Mohamed Hmamouchi、Hakima Es-Samti

  DOI：10.1016/j.tet.2007.09.016

  日期：2007.11

  Abstract Efficient routes towards the austrodorane skeleton from the labdane diterpene (−)-sclareol (22) are described. The processes, based on pinacol rearrangement, take place with complete diastereoselectivity. Utilizing these, the marine nor-sesquiterpenes (+)-austrodoral (1) and (+)-austrodoric acid (2) have been prepared from 22. Ketone 19, a key intermediate in the synthesis of rearranged cytotoxic

  摘要 描述了从劳丹烯二萜 (-)-香紫苏醇 (22) 到南芥骨架的有效途径。基于频哪醇重排的过程以完全的非对映选择性进行。利用这些，海洋去甲倍半萜 (+)-austrodoral (1) 和 (+)-austrodoric 酸 (2) 已由 22. 酮 19 制备，它是合成重排细胞毒性二萜内酯（如去甲缩松）的关键中间体(3)、也已制备成中等产量。