(1R,4S,5S)-4,6,6-Trimethyl-4-vinylbicyclo<3.1.1>heptan-2-one | 128261-62-1

• 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: (1R,4S,5S)-4,6,6-Trimethyl-4-vinylbicyclo<3.1.1>heptan-2-one
• 英文别名: (1R,4S,5R)-(+)-4,6,6-trimethyl-4-vinylbicyclo<3.1.1>heptan-2-one；(1R,4S,5S)-4-ethenyl-4,6,6-trimethylbicyclo[3.1.1]heptan-2-one
• CAS: 128261-62-1
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: UKOUVTROMKPGBE-PTOFAABTSA-N

物化性质

• 沸点：
  231.7±9.0 °C(Predicted)
• 密度：
  0.993±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,4S,5S)-4,6,6-Trimethyl-4-vinylbicyclo<3.1.1>heptan-2-one 在 三氟化硼乙醚 、 zinc diacetate 作用下， 以 乙酸酐 为溶剂， 反应 20.0h， 以68%的产率得到(4S,5S)-1-Acetoxy-4-isopropyl-5-methyl-5-vinyl-1-cyclohexene
  参考文献：
  名称：

  Kato, Michiharu; Vogler, Bernhard; Tooyama, Youichi, Chemistry Letters, 1990, p. 151 - 154

  摘要：

  DOI：
• 作为产物：
  描述：

  beta-pinene 在 甲醇 、 copper(l) iodide 、 copper(I) bromide dimethylsulfide complex 、 甲烷磺酸 、 氨 、 乙酸酐 、 lithium 、 臭氧 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 95.33h， 生成 (1R,4S,5S)-4,6,6-Trimethyl-4-vinylbicyclo<3.1.1>heptan-2-one
  参考文献：
  名称：

  The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes

  摘要：

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.

  DOI：

  10.1021/jo00025a023

文献信息

• Total Syntheses of Sarcandrolide J and Shizukaol D: Lindenane Sesquiterpenoid [4+2] Dimers
  作者：Changchun Yuan、Biao Du、Heping Deng、Yi Man、Bo Liu

  DOI：10.1002/anie.201610484

  日期：2017.1.9

  The syntheses of members of a family of lindenane sesquiterpenoid [4+2] dimers led to the total syntheses of sarcandrolide J and shizukaol D. Inspired by a modified biosynthetic pathway, a cascade featuring furan formation/alkene isomerization/Diels–Alder cycloaddition was devised to construct the congested polycyclic architecture of the target molecules with the correct stereochemistry. This study

  茚满倍半萜类 [4+2] 二聚体家族成员的合成导致了 sarcandrolide J 和 Shizukaol D 的全合成。 受改良的生物合成途径的启发，设计了以呋喃形成/烯烃异构化/Diels-Alder 环加成为特征的级联反应以正确的立体化学构建目标分子的拥塞多环结构。这项研究为这一天然产物家族开辟了开创性的合成入口，并为充分探索其生物学功能铺平了道路。
• A Stereocontrolled Synthesis of (4a<i>S</i>, 8a<i>R</i>)-(+)-7,7- Ethylenedioxy-4,4,8a-trimethyloctahydro-2(1<i>H</i>)-naphthalenone
  作者：Michiharu Kato、Masataka Watanabe、Yoshiaki Masuda

  DOI：10.1246/bcsj.65.2071

  日期：1992.8

  A stereocontrolled synthesis of (4aS, 8aR)-(+)-7,7-ethylenedioxy-4,4,8a-trimethyloctahydro-2(1H)-naphthalenone, which will act as a versatile building block for the asymmetric synthesis of natural products possessing a trans-1,1,4a-trimethyldecalin unit, was accomplished starting with (1R,4S,5R)-(+)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]-heptan-2-one, readily accessible from (+)-nopinone.

  (4aS, 8aR)-(+)-7,7-ethylenedioxy-4,4,8a-trimethyloctahydro-2(1H)-naphthalenone 的立体控制合成，它将作为天然产物不对称合成的通用构件具有反式-1,1,4a-三甲基十氢化萘单元，由 (1R,4S,5R)-(+)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]-heptan-2- 开始完成一，容易从 (+)-nopinone 获得。
• Deprotection of 1,3-oxathiolanes to ketones promoted by base
  作者：Biao Du、Changchun Yuan、Langzhong Zhang、Li Yang、Bo Liu

  DOI：10.1016/j.tetlet.2013.02.053

  日期：2013.5

  A variety of 1,3-oxathiolanes can be easily converted to the corresponding ketones in good yields with LTMP in THF. This deprotection methodology shows satisfactory chemoselectivity when other protecting groups, such as dimethylketal, 1,3-dioxolane, 1,3-dithiane, and other acid-sensitive groups, are present within the same substrates. (C) 2013 Elsevier Ltd. All rights reserved.
• Bioinspired Total Synthesis of Bolivianine: A Diels– Alder/Intramolecular Hetero-Diels–Alder Cascade Approach
  作者：Changchun Yuan、Biao Du、Li Yang、Bo Liu

  DOI：10.1021/ja4040335

  日期：2013.6.26

  We report the first total synthesis of bolivanine in a 14 step pathway involving the synthesis of onoseriolide. Our synthesis features a palladium-catalyzed intramolecular cyclopropanation involving an allylic metal carbene and a Diels-Alder/intramolecular hetero-Diels-Alder cascade, allowing the single-step assembly of a tricyclic system with proper configuration. The synthetic efforts validate our modified biogenetic hypothesis and allow us to confirm the absolute configuration of bolivianine.
• KATO, MICHIHARU;VOGLER, BERNHARD;TOOYAMA, YOUICHI;YOSHIKOSHI, AKIRA, CHEM. LETT.,(1990) N, C. 151-154
  作者：KATO, MICHIHARU、VOGLER, BERNHARD、TOOYAMA, YOUICHI、YOSHIKOSHI, AKIRA

  DOI：——

  日期：——