2-[2-(3-isopropyl-2-methoxyphenyl)ethyl]-3-methylcyclohex-2-en-1-one | 1245920-23-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-[2-(3-isopropyl-2-methoxyphenyl)ethyl]-3-methylcyclohex-2-en-1-one
• 英文别名: 2-[2-(3-isopropyl-2-methoxyphenyl)ethyl]-3-methylcyclohex-2-enone；2-[2-(2-Methoxy-3-propan-2-ylphenyl)ethyl]-3-methylcyclohex-2-en-1-one
• CAS: 1245920-23-3
• 化学式: C₁₉H₂₆O₂
• 分子量: 286.414
• InChiKey: CYAYRBZQOAKHGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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-[2-(3-isopropyl-2-methoxyphenyl)ethyl]-3-methylcyclohex-2-en-1-one 在 dimethyl sulfide borane 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 间氯过氧苯甲酸 、 (R)-2-甲基-CBS-恶唑硼烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Cationic cyclization of keto-epoxides mediated by zirconium(IV) tetrachloride: diastereoselective synthesis of cis-decalinols

  摘要：

  10-Methyl-cis-9-decalinols are important motifs in several natural products and key intermediates in total synthesis. Herein, we wish to describe a highly chemo- and diastereoselective cyclization of ketoepoxides leading to 10-methyl-cis-9-decalinols. This method based on the use of zirconium(IV) tetrachloride permits the access to a wide variety of cis-decalinols in good to excellent yields. The cationic cyclization could also be performed with chiral keto-epoxide with complete control of the diastereoselectivity affording cis-bicyclic tertiary alcohol with good enantiomeric excess. The chemo- and the diastereoselectivity are assumed to result from the ability of Zr(IV) to generate highly stable bidentic complexes with alpha-hydroxy-ketone intermediates. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.050
• 作为产物：
  描述：

  methyl 6-(3-isopropyl-2-methoxyphenyl)-3-oxo-2-(3-oxo-butyl)hexanoate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 3.5h， 以90%的产率得到2-[2-(3-isopropyl-2-methoxyphenyl)ethyl]-3-methylcyclohex-2-en-1-one
  参考文献：
  名称：

  通过对2-烯基-1,3-二硫杂环戊烷的新型阳离子环化，对（+/-）-雷公藤甲素进行非对映选择性正式全合成。

  摘要：

  描述了雷公藤甲素的简明和非对映选择性正式全合成，雷公藤甲素是具有广泛生物学特性的天然产物。关键反应是TMSOTf作为路易斯酸诱导的2-烯基-1,3-二硫杂环戊烷前体的6-内-Trig阳离子环空化。

  DOI：

  10.1039/c0cc00250j

文献信息

• Cationic Cyclization of 2-Alkenyl-1,3-dithiolanes: Diastereoselective Synthesis of <i>trans</i>-Decalins
  作者：Sylvie Goncalves、Stefano Santoro、Marc Nicolas、Alain Wagner、Philippe Maillos、Fahmi Himo、Rachid Baati

  DOI：10.1021/jo2001116

  日期：2011.5.6

  TMSOTf, triggering the cationic 6-endo-trig cyclization, and closes after C−C bond formation and diastereoselective protonation to terminate the process. DFT calculations confirm this mechanistic proposal and provide a rationale for the observed diastereoselectivity. The reaction tolerates a wide range of functionalities and nucleophilic partners within the substrate. We have also shown that the one-pot

  前所未有的和高度非对映6-内-三角函数的2-链烯基-1,3-二硫戊环化已经发展得到反式-decalins，存在于众多的二-和三萜类化合物的一个重要的支架。这个6-的新颖性内切- trig的环化手段在涉及2-链烯基-1,3-二硫戊环的分步机构，作为一个新的潜引发剂。有人建议，在硫缩酮暂时打开将TMSOTf的影响下，引发阳离子6-内- TRIG环化，并在C-C键形成和非对映选择性质子化后关闭，以终止该过程。DFT计算证实了这一机理性建议，并为观察到的非对映选择性提供了理论依据。该反应可耐受底物内的多种功能和亲核伴侣。我们还表明，一锅煮6-内- trig的环化，随后在原位1,3-二硫戊直接脱保护得到相应的酮。这一改进使得雷公藤多酚的总合成最短，雷公藤内酯的形式最短。
• An efficient one-pot four-step domino reaction for the synthesis of C2-substituted 3-methylcyclohex-2-enones
  作者：Sylvie Goncalves、Philippe Maillos、Marc Nicolas、Alain Wagner、Rachid Baati

  DOI：10.1016/j.tet.2010.07.029

  日期：2010.9

  An efficient one-pot four-step domino reaction of substituted beta-ketoesters has been optimized giving rise to a large panel of C2-substituted 3-methylcyclohex-2-enones, an important scaffold for the preparation of various initiators for cationic or radical cyclizations. The developed methodology is quite general and applicable to a wide range of beta-ketoester substrates, allowing the introduction of various functionalities at the C2 position of the 3-methylcyclohex-2-enones, in good to excellent yields. (C) 2010 Elsevier Ltd. All rights reserved.
• Cationic cyclization of keto-epoxides mediated by zirconium(IV) tetrachloride: diastereoselective synthesis of cis-decalinols
  作者：Sylvie Goncalves、Marc Nicolas、Philippe Maillos、Rachid Baati

  DOI：10.1016/j.tet.2011.08.050

  日期：2011.10

  10-Methyl-cis-9-decalinols are important motifs in several natural products and key intermediates in total synthesis. Herein, we wish to describe a highly chemo- and diastereoselective cyclization of ketoepoxides leading to 10-methyl-cis-9-decalinols. This method based on the use of zirconium(IV) tetrachloride permits the access to a wide variety of cis-decalinols in good to excellent yields. The cationic cyclization could also be performed with chiral keto-epoxide with complete control of the diastereoselectivity affording cis-bicyclic tertiary alcohol with good enantiomeric excess. The chemo- and the diastereoselectivity are assumed to result from the ability of Zr(IV) to generate highly stable bidentic complexes with alpha-hydroxy-ketone intermediates. (C) 2011 Elsevier Ltd. All rights reserved.
• Diastereoselective formal total synthesis of (±)-triptolide via a novel cationic cyclization of 2-alkenyl-1,3-dithiolane
  作者：Sylvie Goncalves、Paul Hellier、Marc Nicolas、Alain Wagner、Rachid Baati

  DOI：10.1039/c0cc00250j

  日期：——

  A concise and diastereoselective formal total synthesis of triptolide, a natural product with a wide range of biological properties, is described. The key reaction is an unprecedented 6-endo-Trig cationic cyclization of a 2-alkenyl-1,3-dithiolane precursor induced by TMSOTf as Lewis acid.

  描述了雷公藤甲素的简明和非对映选择性正式全合成，雷公藤甲素是具有广泛生物学特性的天然产物。关键反应是TMSOTf作为路易斯酸诱导的2-烯基-1,3-二硫杂环戊烷前体的6-内-Trig阳离子环空化。