(S)-4-Acetoxy-2-cyclohexenone | 132513-02-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-4-Acetoxy-2-cyclohexenone
• 英文别名: (S)-(-)-4-acetoxy-2-cyclohexen-1-one；[(1S)-4-oxocyclohex-2-en-1-yl] acetate
• CAS: 132513-02-1
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: KBIDPOQYMJNQCH-MRVPVSSYSA-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：

  (S)-4-Acetoxy-2-cyclohexenone 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 生成 (S)-(-)-4-hydroxy-2-cyclohexan-1-one
  参考文献：
  名称：

  （R）和（S）-4-羟基-2-环己烯酮及其衍生物的不对称合成

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)97138-7
• 作为产物：
  描述：

  (7S,8S)-7-[(R)-(4-methylphenyl)sulfinyl]-1,4-dioxaspiro[4.5]decan-8-ol 在 硫酸 、 sodium acetate 、 silica gel 作用下， 生成 (S)-4-Acetoxy-2-cyclohexenone
  参考文献：
  名称：

  （R）和（S）-4-羟基-2-环己烯酮及其衍生物的不对称合成

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)97138-7

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。
• A rule to predict which enantiomer of a secondary alcohol reacts faster in reactions catalyzed by cholesterol esterase, lipase from Pseudomonas cepacia, and lipase from Candida rugosa
  作者：Romas J. Kazlauskas、Alexandra N. E. Weissfloch、Aviva T. Rappaport、Louis A. Cuccia

  DOI：10.1021/jo00008a016

  日期：1991.4

  The enantioselectivity of the title enzymes for more than 130 esters of secondary alcohols is correlated by a rule based on the sizes of the substituents at the stereocenter. This rule predicts which enantiomer of a racemic secondary alcohol reacts faster for 14 of 15 substrates of cholesterol esterase (CE), 63 of 64 substrates of lipase from Pseudomonas cepacia (PCL), and 51 of 55 cyclic substrates of lipase from Candida rugosa (CRL). The enantioselectivity of CRL for acyclic secondary alcohols is not reliably predicted by this rule. This rule implies that the most efficiently resolved substrates are those having substituents which differ significantly in size. This hypothesis was used to design syntheses of two chiral synthons: esters of (R)-lactic acid and (S)-(-)-4-acetoxy-2-cyclohexen-1-one, 70. As predicted, the acetate group of the methyl ester of lactyl acetate was hydrolyzed by PCL with low enantioselectivity because the two substituents, CH3 and C(O)OCH3, are similar in size. To improve the enantioselectivity, the methyl ester was replaced by a tert-butyl ester. The acetate group of the tert-butyl ester of lactyl acetate was hydrolyzed with high enantioselectivity (E > 50). Enantiomerically pure (R)-(+)-tert-butyl lactate (> 98% ee, 6.4 g) was prepared by kinetic resolution. For the second example, low enantioselectivity (E < 3) was observed in the hydrolysis of cis-1,4-diacetoxycyclohex-2-ene, a meso substrate where the two substituents, CH2CH2 and CH = CH, are similar in size. To improve enantioselectivity, the size of the CH = CH substituent was increased by addition of Br2. The new substrate was hydrolyzed with high enantioselectivity (E > 65) using either CE or CRL. Enantiomerically pure 70 (98% ee) was obtained after removal of the bromines with zinc and oxidation with CrO3/pyridine.