(R)-4-acetoxy-2-cyclohexen-1-one | 132658-89-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-4-acetoxy-2-cyclohexen-1-one
• 英文别名: (R)-4-Acetoxy-2-cyclohexenone；[(1R)-4-oxocyclohex-2-en-1-yl] acetate
• CAS: 132658-89-0
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: KBIDPOQYMJNQCH-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 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：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-4-acetoxy-2-cyclohexen-1-one 在 potassium carbonate 、 silver(l) oxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.17h， 生成 (R)-4-benzyloxy-2-cyclohexen-1-one
  参考文献：
  名称：

  Enantioselective Synthesis of (R)- and (S)-4-Benzyloxy-2-cyclohexen-1-one

  摘要：

  DOI：

  10.1021/jo001413l
• 作为产物：
  描述：

  [(1R,2S)-2-benzylsulfanyl-4-oxocyclohexyl] acetate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 (R)-4-acetoxy-2-cyclohexen-1-one
  参考文献：
  名称：

  Facile biocatalytic syntheses of optically active 4-hydroxycyclohex-2-enone and 4-benzylthiacyclopent-2-enone

  摘要：

  Novozyme 435(R) (Candida antarctica Lipase B) effects the kinetic resolution of both 3-benzylthia-4-hydroxycyclopentanone and its six-membered ring analogue, providing a novel route to both enantiomers of 4-benzylthiacyclopent-2-enone and the two enantiomers of 4-hydroxycyclohex-2-enone, all in a state of very high optical purity. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.07.042

文献信息

• The thio-adduct facilitated, enzymatic kinetic resolution of 4-hydroxycyclopentenone and 4-hydroxycyclohexenone
  作者：Aisling O'Byrne、Cian Murray、Dearbhla Keegan、Carole Palacio、Paul Evans、Ben S. Morgan

  DOI：10.1039/b916506a

  日期：——

  The addition of 3,4-dimethoxybenzyl thiol 8, as a benzyl thiol surrogate, to racemic 4-hydroxycyclopent-2-enone 2 and 4-hydroxycyclohex-2-enone 15 gave the corresponding cis-adducts (±)-3-(3,4-dimethoxybenzylthio)-4-hydroxycyclopentanone 4b and (±)-3-(3,4-dimethoxybenzylthio)-4-hydroxycyclohexanone 16 with good diastereocontrol. In both cases, subsequent treatment with vinyl acetate, in the presence of a lipase enabled enantiomer resolution. Thus, (+)-16 and the acetate of its enantiomer, (–)-(1R,2S)-2-(3,4-dimethoxybenzylthio)-4-oxocyclohexyl acetate, (–)-17 were isolated in 98% enantiomeric excess. Based on the 1,4-dioxygenation pattern, (–)-17 can be used to prepare both enantiomers of 4-(tert-butyldimethylsilyloxy)cyclohex-2-enone 19. Firstly, saponification, with a sub-stoichiometric amount of NaOMe, followed by a one-pot silyl ether formation–sulfide elimination sequence gave (+)-19. Then using the same starting material a 6-step sequence, featuring a diastereoselective NaBH4 reduction and a Cope-type sulfoxide elimination, gave (–)-19.

  将 3,4-二甲氧基苄基硫醇 8（作为苄基硫醇的代用品）加到外消旋 4-羟基环戊-2-烯酮 2 和 4-羟基环己-2-烯酮 15 中，可得到相应的顺式加成物 (±)-3-(3、(±)-3-(3,4-二甲氧基苄硫基)-4-羟基环戊酮 4b 和 (±)-3-(3,4-二甲氧基苄硫基)-4-羟基环己酮 16。在这两种情况下，随后在脂肪酶存在下用乙酸乙烯酯进行处理，都能实现对映体的解析。因此，(+)-16 及其对映体(-)-(1R,2S)-2-(3,4-二甲氧基苄硫基)-4-氧代环己基乙酸酯(-)-17 的对映体过量率为 98%。根据 1,4-二氧代模式，(-)-17 可用于制备 4-(叔丁基二甲基硅氧基)环己-2-烯酮 19 的两种对映体。首先，使用亚几何量的 NaOMe 进行皂化，然后通过硅醚形成-硫化物消除的一锅式顺序制备出 (+)-19。然后使用相同的起始原料，经过 6 个步骤，包括非对映选择性 NaBH4 还原和 Cope 型亚砜消除，得到了 (-)-19。
• Asymmetric synthesis of (R) and (S)-4-hydroxy-2-cyclohexenone and derivatives
  作者：M Carmen Carreño、José L García Ruano、Mercedes Garrido、M Pilar Ruiza、Guy Solladié

  DOI：10.1016/s0040-4039(00)97138-7

  日期：1990.1

  The asymmetric syntheses of both enantiomers of 4-hydroxy-2-cyclohexenone and their O-acetyl and O-benzyl derivatives are reported. DIBAL and ZnCl2/DIBAL stereosetective reductions of the keto- sulfoxides resulting in the sulfinylation of 1,4-cyclohexanedione ethylene monoketal are the key steps in these syntheses.

  据报道4-羟基-2-环己烯酮的两种对映异构体及其O-乙酰基和O-苄基衍生物的不对称合成。酮亚砜的DIBAL和ZnCl 2 / DIBAL立体定位还原导致1,4-环己二酮亚乙基单缩酮的亚磺酰化是这些合成的关键步骤。
• Asymmetric synthesis of chiral cycloalkenone derivatives <i>via</i> palladium catalysis
  作者：Barry M. Trost、James T. Masters、Jean-Philip Lumb、Dahlia Fateen

  DOI：10.1039/c3sc53250j

  日期：——

  Palladium-catalyzed oxidative desymmetrization enables the efficient synthesis of both enantioenriched cycloalkenone building blocks and diverse epoxyquinoid natural products.

  钯催化的氧化去对称化反应可有效合成手性富集的环烯酮构建块和多样的环氧醌天然产物。
• Facile biocatalytic syntheses of optically active 4-hydroxycyclohex-2-enone and 4-benzylthiacyclopent-2-enone
  作者：Ben S. Morgan、Dorothée Hoenner、Paul Evans、Stanley M. Roberts

  DOI：10.1016/j.tetasy.2004.07.042

  日期：2004.9

  Novozyme 435(R) (Candida antarctica Lipase B) effects the kinetic resolution of both 3-benzylthia-4-hydroxycyclopentanone and its six-membered ring analogue, providing a novel route to both enantiomers of 4-benzylthiacyclopent-2-enone and the two enantiomers of 4-hydroxycyclohex-2-enone, all in a state of very high optical purity. (C) 2004 Elsevier Ltd. All rights reserved.
• Enantioselective Synthesis of (<i>R</i>)- and (<i>S</i>)-4-Benzyloxy-2-cyclohexen-1-one
  作者：Hidetaka Suzuki、Naoki Yamazaki、Chihiro Kibayashi

  DOI：10.1021/jo001413l

  日期：2001.2.1