ethyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate | 127039-97-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate
• CAS: 127039-97-8
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: OMJKTYGETUSMQJ-UHFFFAOYSA-N

物化性质

• 沸点：
  334.4±12.0 °C(Predicted)
• 密度：
  1.107±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate 在 dirhodium tetraacetate 、 sodium hydroxide 、 对甲苯磺酰叠氮 、 硫酸 、 potassium carbonate 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 22.0h， 生成 1-oxaspiro<4.5>decan-3-one
  参考文献：
  名称：

  A short protocol for the synthesis of spirocyclic tetrahydrofurans via intramolecular O–H insertion

  摘要：

  The conversion of cyclic ketones to functionalised spirocyclic tetrahydrofurans via a three-step sequence of acetoacetate ester dianion-aldol reaction, diazo-transfer and carbene O-H insertion is described. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00097-7
• 作为产物：
  描述：

  溴乙酸乙酯 、 环己酮 在 samarium diiodide 作用下， 生成 ethyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate
  参考文献：
  名称：

  A Preparation ofβ-Oxoester Enolate Equivalents from SmI₂andα-Bromoalkanoates

  摘要：

  将乙基溴乙酸酯在 -50 °C 下与两摩尔当量的二碘钕处理 15 分钟，使用 THF 作为溶剂，产生β-氧酯烯醇等效物；该试剂与酮或醛反应，能够以优异的产率生成δ-羟基-β-氧酯。

  DOI：

  10.1246/cl.1995.197

文献信息

• A Preparation of<i>β</i>-Oxoester Enolate Equivalents from SmI₂and<i>α</i>-Bromoalkanoates
  作者：Kiitiro Utimoto、Toshiki Matsui、Tsutomu Takai、Seijiro Matsubara

  DOI：10.1246/cl.1995.197

  日期：1995.3

  A treatment of ethyl bromoacetate with two molar equivalent of samarium diiodide at −50 °C for 15 min in THF produces a β-oxoester enolate equivalent; the reagent reacts with ketones or aldehydes to give δ-hydroxy-β-oxoesters in excellent yields.

  将乙基溴乙酸酯在 -50 °C 下与两摩尔当量的二碘钕处理 15 分钟，使用 THF 作为溶剂，产生β-氧酯烯醇等效物；该试剂与酮或醛反应，能够以优异的产率生成δ-羟基-β-氧酯。
• Rhodium(II)- and Copper(I)-Catalyzed Intramolecular Carbon-Hydrogen Bond Insertions with Metal Carbenoids Derived from Diazo Ketones
  作者：Paul Müller、Esther Maîtrejean

  DOI：10.1135/cccc19991807

  日期：——

  The decomposition of diazo ketones in the presence of Rh(II) and Cu(I) catalysts affords products of C-H bond insertion in high yields. The effect of structural variation on intramolecular and transannular C-H insertions of diazo ketones has been investigated. The enantioselectivity of the insertion was examined with 15 chiral catalysts of different structural types. It was low in all cases. The poor enantioselectivity of the insertion of diazo ketones in comparison to that obtained in insertions of diazo esters and diazo amides is attributed to two factors: The oxocarbenes derived from diazo esters and diazo amides are stabilized by resonance of the carbonyl group with the heteroatom. Furthermore, the conformational constraints which must be overcome in order to reach the transition state for intramolecular insertion are lower in the case of carbenes derived from diazo ketones than in those from diazo esters and amides owing to the higher rotational barriers of amides and esters in comparison with that of ketones. This results in an earlier, and therefore less selective transition state for insertion of diazo ketones.

  在Rh(II)和Cu(I)催化剂存在的情况下，重氮酮的分解产物以高收率形成C-H键插入产物。研究了结构变化对重氮酮的分子内和跨环C-H插入的影响。使用了15种不同结构类型的手性催化剂来检验插入的对映选择性。在所有情况下，对映选择性都很低。与重氮酯和重氮酰胺的插入相比，重氮酮的插入的对映选择性较差，这归因于两个因素：重氮酯和重氮酰胺产生的氧代碳烯通过羰基与杂原子的共振来稳定。此外，为达到分子内插入的过渡态必须克服的构象约束比起自重氮酮派生的碳烯而言，自重氮酯和酰胺派生的碳烯具有更低的旋转能垒，导致重氮酮插入的过渡态更早，因此选择性更低。
• Regioselective Addition of 1,3-Dicarbonyl Dianions to Carbonyl Compounds: One Pot Lactonization and Ketalization of δ-Hydroxy-β-keto Esters to Protected Pyrone Derivatives
  作者：Manas K. Ghorai、Sandipan Halder、Sauvik Samanta

  DOI：10.1071/ch12062

  日期：——

  strategy for the synthesis of 6-substituted-2-pyrone derivatives, by BF3·OEt2 mediated one pot cyclization and keto-protection of δ-hydroxy-β-keto esters, obtained via regioselective addition of 1,3-dicarbonyl dianion of ethyl acetoacetate to aldehydes and ketones is described.

  一种简单有效的策略，通过BF 3 ·OEt 2介导的δ-羟基-β-酮酯的一锅环化和酮保护，通过区域选择性添加1,3获得6-取代的2-吡喃酮衍生物描述了乙酰乙酸乙酯的-二羰基二价阴离子对醛和酮。
• Tin analogs of the vinylogous reformatsky reaction. Regio- and stereochemical considerations
  作者：RuLin Fan、Tomas Hudlicky

  DOI：10.1016/s0040-4039(01)93792-x

  日期：1989.1

  Ethyl-4-(tri-n-butyltin)-3-methyl crotonate and ethyl 4-(tri-n-butyltin)-3-methoxycrotonate were condensed with benzaldehyde and cyclohexanone. The regio- and stereochemical profiles were determined in an effort to control the course of dienolate additions to carbonyl compounds under acid-catalyzed conditions.

  将4-（三正丁基锡）-3-巴豆酸乙酯和4-（三正丁基锡）-3-甲氧基巴豆酸乙酯与苯甲醛和环己酮缩合。为了控制在酸催化条件下向羰基化合物中二烯酸酯添加的过程，确定了区域和立体化学分布。
• FAN, RULIN;HUDECKY, TOMAS, TETRAHEDRON LETT., 30,(1989) N1, C. 5533-5536
  作者：FAN, RULIN、HUDECKY, TOMAS

  DOI：——

  日期：——