(S)-6-methyl-6-(4-methyl-pent-4-enyl)-1-vinyl-cyclohexene | 275825-03-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (S)-6-methyl-6-(4-methyl-pent-4-enyl)-1-vinyl-cyclohexene
• 英文别名: (S)-6-methyl-6-(4-methylpent-4-enyl)-1-vinylcyclohex-1-ene；(S)-6-methyl-6-(4-methylpent-4-en-1-yl)-1-vinylcyclohex-1-ene；(6S)-1-ethenyl-6-methyl-6-(4-methylpent-4-enyl)cyclohexene
• CAS: 275825-03-1
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: IVAOTBXXXUFSSE-HNNXBMFYSA-N

物化性质

• 沸点：
  267.6±7.0 °C(Predicted)
• 密度：
  0.867±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (S)-6-methyl-6-(4-methyl-pent-4-enyl)-1-vinyl-cyclohexene 在 二氯乙基铝 aluminium hydride 、 sodium tetrahydroborate 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 生成 Toluene-4-sulfonic acid (1R,2R,5S,8aR)-1,2,5-trimethyl-5-(4-methyl-pent-4-enyl)-1,2,3,5,6,7,8,8a-octahydro-naphthalen-1-ylmethyl ester
  参考文献：
  名称：

  Concise asymmetric synthesis of dysidiolide

  摘要：

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized via intermolecular Diels-Alder reaction of the triene 4 with crotonaldehyde and construction of a quaternary carbon center by methylation of the exocyclic enolate. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00078-2
• 作为产物：
  描述：

  (S)-6-methyl-6-(4-methylbenzenesulfonyloxypropyl)-1,4-dioxaspiro[4.5]decane 在 copper(l) iodide cerium(III) chloride 、 4-甲基苯磺酸吡啶 、 sodium iodide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 生成 (S)-6-methyl-6-(4-methyl-pent-4-enyl)-1-vinyl-cyclohexene
  参考文献：
  名称：

  Concise asymmetric synthesis of dysidiolide

  摘要：

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized via intermolecular Diels-Alder reaction of the triene 4 with crotonaldehyde and construction of a quaternary carbon center by methylation of the exocyclic enolate. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00078-2

文献信息

• Solid-Phase Synthesis of Dysidiolide-Derived Protein Phosphatase Inhibitors
  作者：Dirk Brohm、Nicolas Philippe、Susanne Metzger、Ajay Bhargava、Oliver Müller、Folker Lieb、Herbert Waldmann

  DOI：10.1021/ja027609f

  日期：2002.11.1

  higher investment in the development of the corresponding syntheses. This approach requires the development of complex multistep reaction sequences on the solid phase. Employing the protein phosphatase Cdc25 inhibitor dysidiolide as an example, we demonstrate that this goal can be achieved successfully. The reaction sequences developed led to dysidiolide analogues in overall 8-12 linear steps with

  具有生物活性的天然产物可以被视为化合物库开发的结构空间中进化选择和生物学验证的起点。对于围绕给定的天然产物设计和合成的文库，可以预期更高的命中率和生物学相关命中的识别，从而证明可能对相应合成的开发进行更高的投资是合理的。这种方法需要在固相上开发复杂的多步反应序列。以蛋白磷酸酶 Cdc25 抑制剂dysidiolide 为例，我们证明这一目标可以成功实现。所开发的反应序列导致在整个 8-12 个线性步骤中产生双碘内酯类似物，固体支持物上的最长序列达到 11 个连续转化。以6%至27%的总产率和从100mg树脂开始的数毫克量获得所需产物。所应用的转化包括广泛用于有机合成的各种非常不同的反应类型（即，使用可去除手性助剂的不对称环加成、不同的有机金属转化、烯化反应、不同的氧化反应、酸性水解和亲核取代）。对合成的八种双碘内酯类似物的生物学研究表明，它们在低微摩尔范围内抑制 Cdc25C，IC(50)
• Stereoselective Alkylation of Allylic Alcohols: Tandem Ethylation and Functionalization
  作者：Pragna Pratic Das、Ivan L. Lysenko、Jin Kun Cha

  DOI：10.1002/anie.201104331

  日期：2011.9.26

  A versatile formal SN2′ alkylation of allylic alcohols has been devised by means of the Kulinkovich reagent and in situ elaboration of the presumed alkyltitanium intermediates with electrophiles (see scheme). The utility of this method has been demonstrated in the stereoselective construction of all‐carbon quaternary centers.

  一种多功能正式小号Ñ 2'烯丙基醇的烷基化已被Kulinkovich试剂的装置和在与亲电子推定alkyltitanium中间体的原位阐述设计（参见方案）。该方法的效用已在全碳四元中心的立体选择性构造中得到证明。
• Stereoconvergent route to chiral cyclohexenone building blocks: formal synthesis of (−)-dysidiolide
  作者：Gamal A. I. Moustafa、Yasumasa Kamada、Tetsuaki Tanaka、Takehiko Yoshimitsu

  DOI：10.1039/c2ob26532j

  日期：——

  carbocycles through a combination of regioselective catalytic asymmetric reduction and alkylative remote stereoinduction. The present stereoconvergent strategy has allowed the formal synthesis of bioactive (−)-dysidiolide.

  据报道立体聚合接近手性碳环结构单元。由四个立体异构体（即外消旋体ca）组成的6-（3'-羟基-4'-甲基戊-4'-烯基）-3-甲氧基环己-2-烯酮（1）。通过区域选择性催化不对称还原和烷基化远程立体诱导的组合，将1：1非对映异构体转化为对映体纯的碳环。当前的立体收敛策略已经允许生物活性的（-）-二氢化茚化物的正式合成。
• Synthesis of the novel analogues of dysidiolide and their structure–activity relationship
  作者：Masato Takahashi、Kosuke Dodo、Yoshikazu Sugimoto、Yoshimi Aoyagi、Yuji Yamada、Yuichi Hashimoto、Ryuichi Shirai

  DOI：10.1016/s0960-894x(00)00527-8

  日期：2000.11

  The novel analogues of natural cdc25A inhibitor dysidiolide were synthesized. To investigate the structure-activity relationship, the inhibitory activity to enzyme and cell cycle was examined. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Concise asymmetric synthesis of dysidiolide
  作者：Masato Takahashi、Kosuke Dodo、Yuichi Hashimoto、Ryuichi Shirai

  DOI：10.1016/s0040-4039(00)00078-2

  日期：2000.3

  The cdc25A protein phosphatase inhibitor dysidiolide (1) has been synthesized via intermolecular Diels-Alder reaction of the triene 4 with crotonaldehyde and construction of a quaternary carbon center by methylation of the exocyclic enolate. (C) 2000 Elsevier Science Ltd. All rights reserved.