(S)-(+)-5-[1-(hydroxymethyl)vinyl]-2-methyl-cyclohex-2-enone

• 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: (S)-(+)-5-[1-(hydroxymethyl)vinyl]-2-methyl-cyclohex-2-enone
• 英文别名: (+)-10-hydroxycarvone；(5S)-5-(3-hydroxyprop-1-en-2-yl)-2-methylcyclohex-2-en-1-one
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: SPYNQWDBZDOAGZ-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  2
• 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：

  (S)-(+)-5-[1-(hydroxymethyl)vinyl]-2-methyl-cyclohex-2-enone 在 sodium carbonate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以60%的产率得到(+)-(5S)-8,9-epoxy-10-hydroxycarvone
  参考文献：
  名称：

  Ti(III)-Promoted Radical Cyclization of Epoxy Enones. Total Synthesis of (+)-Paeonisuffrone

  摘要：

  The total synthesis of (+)-paeonisuffrone starting from (+)-10-hydroxycarvone is described. The key step of our synthetic strategy is a titanium-catalyzed stereoselective cyclization initiated by epoxide opening through electron transfer. This reaction stereoselectively affords the highly oxygenated pinane skeleton present in the target molecule and opens a new and effective approach to the synthesis of the complex, biologically active terpenoids isolated from the roots of the Chinese paeony (Paeonia albiflora Pallas and Paeonia suffruticosa Andrews).

  DOI：

  10.1021/jo8026033
• 作为产物：
  描述：

  右旋香芹酮 在 sodium hypochlorite 、 potassium dihydrogenphosphate 、 水 、 碳酸氢钠 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 54.0h， 生成 (S)-(+)-5-[1-(hydroxymethyl)vinyl]-2-methyl-cyclohex-2-enone
  参考文献：
  名称：

  Sesterterpenoid Ansellones A和B，以及Phorbadione的总合成

  摘要：

  Ansellane型酯类萜类化合物包括ansellones A-G和（+）-phorbadione是结构新颖的海洋次级代谢产物，具有抗癌和抗HIV活性。从（+）-香紫苏内酯起16至23步完成了三个结构上具有代表性的成员（-）-杏仁糖A和B和（+）-佛巴丹酮的第一个不对称全合成。这条路线的特点是通过内部醇亲核试剂以1,4加成方式（S N 2'）对乙烯基环氧化合物进行第一次区域选择性环化。此外，烯丙基CH氧化是在合成（-）-鞣酸A和（+）-佛手瓜酮的后期进行的。预期该策略可适用于其他茴香油酯类萜类化合物的合成。

  DOI：

  10.1002/anie.201701879

文献信息

• Ti(III)-promoted cyclizations. Application to the synthesis of (E)-endo-bergamoten-12-oic acids. Moth oviposition stimulants isolated from Lycopersicon hirsutum
  作者：Francisco A. Bermejo、Alfonso Fernández Mateos、Andrés Marcos Escribano、Rodrigo Martín Lago、Lydia Mateos Burón、María Rodríguez López、Rosa Rubio González

  DOI：10.1016/j.tet.2006.07.020

  日期：2006.9

  as the key step to access the diol 10 as a convenient starting material of the target molecules. The synthesis of β-(E)-endo-bergamoten-12-oic acid 2a from (+)-8,9-epoxycarvone 8 was successfully achieved by Suzuki–Miyaura coupling of the terminal alkene 20 with β-iodomethacrylate 21c, followed by deprotection and dehydration processes. Moreover, synthesis of the α-(E)-endo-1-hydroxy-bergamoten-12-oic

  环氧树脂烯8的Ti（III）促进的自由基环化被描述为获取二醇10的关键步骤，而二醇10是目标分子的便捷原料。β-（合成ë - ）内-bergamoten十二烷-12-酸2A从（+） - 8,9- epoxycarvone 8通过铃木-宫浦末端烯烃的耦合成功地实现了20与β-iodomethacrylate 21C，接着脱保护和脱水过程。此外，通过二醇的重复伸长过程实现了α-（E）-内-1-羟基-佛手柑-12-油酸衍生物34的合成。10条侧链。
• Functionalized α,α-Dibromo Esters through Claisen Rearrangements of Dibromoketene Acetals
  作者：Nathan J. Dupper、Ohyun Kwon

  DOI：10.1021/acs.orglett.5b00209

  日期：2015.2.20

  Allylic alcohols can be transformed into gamma,delta-unsaturated alpha,alpha-dibromo esters through a two-step process: formation of a bromal-derived mixed acetal, followed by tandem dehydrobromination/Claisen rearrangement. The scope and selectivity of both steps have been investigated. The product alpha,alpha-dibromo esters were subjected to various carbon-carbon bond-forming reactions, oxidations, and lactonizations.
• Ti(III)-Promoted Radical Cyclization of Epoxy Enones. Total Synthesis of (+)-Paeonisuffrone
  作者：María Martín-Rodríguez、Raquel Galán-Fernández、Andrés Marcos-Escribano、Francisco A. Bermejo

  DOI：10.1021/jo8026033

  日期：2009.2.20

  The total synthesis of (+)-paeonisuffrone starting from (+)-10-hydroxycarvone is described. The key step of our synthetic strategy is a titanium-catalyzed stereoselective cyclization initiated by epoxide opening through electron transfer. This reaction stereoselectively affords the highly oxygenated pinane skeleton present in the target molecule and opens a new and effective approach to the synthesis of the complex, biologically active terpenoids isolated from the roots of the Chinese paeony (Paeonia albiflora Pallas and Paeonia suffruticosa Andrews).
• Total Syntheses of Sesterterpenoid Ansellones A and B, and Phorbadione
  作者：Wei Zhang、Hongliang Yao、Jingxun Yu、Zhihong Zhang、Rongbiao Tong

  DOI：10.1002/anie.201701879

  日期：2017.4.18

  ansellones A‐G and (+)‐phorbadione are structurally novel marine secondary metabolites which exhibit anticancer and anti‐HIV activity. The first, asymmetric total syntheses of three structurally representative members, (−)‐ansellones A and B and (+)‐phorbadione, were accomplished in 16–23 steps from (+)‐sclareolide. The route features the first regioselective cyclization of vinyl epoxides with internal

  Ansellane型酯类萜类化合物包括ansellones A-G和（+）-phorbadione是结构新颖的海洋次级代谢产物，具有抗癌和抗HIV活性。从（+）-香紫苏内酯起16至23步完成了三个结构上具有代表性的成员（-）-杏仁糖A和B和（+）-佛巴丹酮的第一个不对称全合成。这条路线的特点是通过内部醇亲核试剂以1,4加成方式（S N 2'）对乙烯基环氧化合物进行第一次区域选择性环化。此外，烯丙基CH氧化是在合成（-）-鞣酸A和（+）-佛手瓜酮的后期进行的。预期该策略可适用于其他茴香油酯类萜类化合物的合成。