(5R,6S)-6-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one

• 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: (5R,6S)-6-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one
• 英文别名: (5R,6S)-6-hydroxy-2-methyl-5-(prop-1-en-2-yl)-2-cyclohexene-1-one；(5r,6s)-6-Hydroxy-5-isopropenyl-2-methylcyclohex-2-en-1-one；(5R,6S)-6-hydroxy-2-methyl-5-prop-1-en-2-ylcyclohex-2-en-1-one
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: YNTOEUGPNLOIEP-SCZZXKLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5R,6S)-6-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one 在 盐酸 、 溶剂黄146 、 儿萘酚硼烷 作用下， 以 二氯甲烷 为溶剂， 反应 49.03h， 生成 cis-6-isopropenyl-3-methyl-2-cyclohexenol
  参考文献：
  名称：

  使用 (+)-香芹酮获得 (+)-ent-大麻二酚的新型衍生物：(+)-ent-CBDP 和 (+)-ent-CBDV 的首次不对称合成

  摘要：

  (−)-大麻二酚 [(−)-CBD] 最近作为治疗神经炎症和其他神经退行性疾病的药物而受到重视；人们对其合成对映体 (+)-CBD 也产生了兴趣，它比天然立体异构体对 CB1/CB2 受体具有更高的亲和力。我们开发了一种廉价的立体选择性途径，使用 (+)-香芹酮作为起始材料来获取ent -CBD 衍生物。除了 (+)-CBD 之外，我们还首次合成了 (+)-cannabidivarin、(+)-cannabidiphorol 以及 C-6/C-8 同系物。

  DOI：

  10.1016/j.tetlet.2021.152891
• 作为产物：
  描述：

  (+)-α-蒎烯 在 lithium aluminium tetrahydride 、 草酰氯 、 双氧水 、 二甲基亚砜 、 sodium hydroxide 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 58.42h， 生成 (5R,6S)-6-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-one
  参考文献：
  名称：

  Highly Potent Activity of (1R,2R,6S)-3-Methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol in Animal Models of Parkinson’s Disease

  摘要：

  (1R,2R,6S)-3-甲基-6-(丙-1-烯-2-基)环己-3-烯-1,2-二醇 1 在 MPTP 和氟哌啶醇动物模型中均表现出强效的抗帕金森症活性。使用化合物 1 能使运动和探索活动几乎完全恢复，其效果与对照药物（左旋多巴）相当。化合物 1 的八个立体异构体均已被合成，且其绝对构型对抗帕金森症活性的影响也已得到验证。

  DOI：

  10.1021/jm2001579

文献信息

• C3 and C6 Modification-Specific OYE Biotransformations of Synthetic Carvones and Sequential BVMO Chemoenzymatic Synthesis of Chiral Caprolactones
  作者：Issa S. Issa、Helen S. Toogood、Linus O. Johannissen、James Raftery、Nigel S. Scrutton、John M. Gardiner

  DOI：10.1002/chem.201805219

  日期：2019.2.26

  with additional substituents at C3 or C6, or both C3 and C6, using three types of OYEs (OYE2, PETNR and OYE3) shows significant impact of both regio‐substitution and the substrate diastereomer. Bioreduction of (−)‐carvone derivatives substituted with a Me and/or OH group at C6 is highly dependent on the diastereomer of the substrate. Derivatives bearing C6 substituents larger than methyl moieties are not

  迄今为止，用于特种中间体的非天然香芹酮衍生物的生物催化修饰范围仍然有限。此外，己内酯是在聚合物工业中具有多种应用的重要原料，因此新型非天然萜酮衍生的生物催化己内酯合成对于工业生物催化材料应用具有潜在价值。使用三种类型的 OYE（OYE2、PETNR 和 OYE3）生物催化还原在 C3 或 C6 或 C3 和 C6 上带有附加取代基的 R-(-)-香芹酮合成类似物，显示了区域取代和底物的显着影响非对映体。在 C6 处被 Me 和/或 OH 基团取代的 (−)-香芹酮衍生物的生物还原高度依赖于底物的非对映异构体。带有大于甲基部分的 C6 取代基的衍生物不是底物。PETNR 与 (6 S )-Me 和 (6 R )-Me 取代的 (−)-香芹酮的计算机对接研究提供了与生物转化结果一致的模型。生物还原产物通过拜耳-维利格单加氧酶 (BVase) CHMO_Phi1 进行有效生物转化，得到具有完全区
• Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis
  作者：Sang-phyo Hong、Harriet A. Lindsay、Tripura Yaramasu、Xiaowei Zhang、Matthias C. McIntosh

  DOI：10.1021/jo010752r

  日期：2002.4.1

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.
• Diastereoselective hydroxylation of titanium enolates with tert-butylhydroperoxide
  作者：M. Schulz、R. Kluge、M. Schüßler、G. Hoffmann

  DOI：10.1016/0040-4020(95)00090-u

  日期：1995.3

  The oxidation of titanium enolates with tert-butylhydroperoxide has been investigated and the main reaction products, the corresponding alpha-hydroxyketones 7a-f, isolated. The highest diastereoselectivities (>95% de) were obtained, when titanium enolates of camphor 2d-6d were employed. For comparison, the oxidation of the enolates with dimethyldioxirane(1) is discussed.
• Highly Potent Activity of (1<i>R</i>,2<i>R</i>,6<i>S</i>)-3-Methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol in Animal Models of Parkinson’s Disease
  作者：Oleg V. Ardashov、Alla V. Pavlova、Irina V. Il’ina、Ekaterina A. Morozova、Dina V. Korchagina、Elena V. Karpova、Konstantin P. Volcho、Tat’yana G. Tolstikova、Nariman F. Salakhutdinov

  DOI：10.1021/jm2001579

  日期：2011.6.9

  (1R,2R,6S)-3-Methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol 1 possesses potent antiparkinsonian activity in both MPTP and haloperidol animal models. The use of compound 1 resulted in nearly full recovery of the locomotor and exploratory activities and was as effective as the comparator agent (levodopa). All eight stereoisomers of compound 1 have been synthesized and the influence of the absolute configuration on the antiparkinsonian activity of compound 1 was shown.

  (1R,2R,6S)-3-甲基-6-(丙-1-烯-2-基)环己-3-烯-1,2-二醇 1 在 MPTP 和氟哌啶醇动物模型中均表现出强效的抗帕金森症活性。使用化合物 1 能使运动和探索活动几乎完全恢复，其效果与对照药物（左旋多巴）相当。化合物 1 的八个立体异构体均已被合成，且其绝对构型对抗帕金森症活性的影响也已得到验证。
• Using (+)-carvone to access novel derivatives of (+)-ent-cannabidiol: The first asymmetric syntheses of (+)-ent-CBDP and (+)-ent-CBDV
  作者：Alexandra E. Golliher、Antonio J. Tenorio、Nina O. Dimauro、Nicolas R. Mairata、F. Omar Holguin、William Maio

  DOI：10.1016/j.tetlet.2021.152891

  日期：2021.3

  has a higher affinity to CB1/CB2 receptors than the natural stereoisomer. We have developed an inexpensive, stereoselective route to access ent-CBD derivatives using (+)-carvone as a starting material. In addition to (+)-CBD, we report the first syntheses of (+)-cannabidivarin, (+)-cannabidiphorol as well as C-6/C-8 homologues.

  (−)-大麻二酚 [(−)-CBD] 最近作为治疗神经炎症和其他神经退行性疾病的药物而受到重视；人们对其合成对映体 (+)-CBD 也产生了兴趣，它比天然立体异构体对 CB1/CB2 受体具有更高的亲和力。我们开发了一种廉价的立体选择性途径，使用 (+)-香芹酮作为起始材料来获取ent -CBD 衍生物。除了 (+)-CBD 之外，我们还首次合成了 (+)-cannabidivarin、(+)-cannabidiphorol 以及 C-6/C-8 同系物。