methyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate | 35468-78-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate
• 英文别名: Methyl-4-(1-hydroxycyclohexyl)-3-oxobutanoat
• CAS: 35468-78-1
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: RXECZAZNFBXNHJ-UHFFFAOYSA-N

物化性质

• 沸点：
  319.3±12.0 °C(predicted)
• 密度：
  1.130±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  methyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate 在 sodium hydroxide 、 2-氯-1-甲基吡啶碘化物 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 (2-Oxo-1-oxaspiro[5.5]undec-3-en-4-yl) 2-bromobenzoate
  参考文献：
  名称：

  用于杂环合成的自由基反应。第3部分：新型螺二内酯，螺内酯-内酰胺和螺内酯-硫代内酯的形成1

  摘要：

  螺二内酯的合成是通过分子内的自由基迈克尔加成而来的，而该迈克尔是从四氢苯甲酸衍生而来的烯醇酯。螺内酯-内酰胺和螺内酯-硫代内酯的合成也被该新反应的范围所涵盖。

  DOI：

  10.1016/s0040-4039(00)00256-2
• 作为产物：
  描述：

  1,3-bis(trimethylsiloxy)-1-methoxybuta-1,3-diene 、 环己酮 在 碘 、 三氟乙酸 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 0.02h， 以45%的产率得到methyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate
  参考文献：
  名称：

  Synthesis of multifunctionalized building blocks via vinylogous addition of Chan’s diene to carbonyl and carbonyl-related electrophiles, mediated by molecular iodine

  摘要：

  The synthesis of multifunctionalized beta-ketoesters has been achieved by using molecular iodine as a catalyst under very mild conditions. The vinylogous addition of Chan's diene 1 to carbonyl and carbonyl-related compounds (aldehydes, ketones, imines and acetals) occurred with high efficiencies and with complete gamma-selectivity, giving a useful method for the synthesis of interesting libraries of different delta-functionalized beta-ketoesters. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.02.036

文献信息

• Aldol Type Condensations of β-Keto Ester Dianions
  作者：Stuart Nicholas Huckin、Larry Weiler

  DOI：10.1139/v74-311

  日期：1974.6.1

  The dianion of methyl acetoacetate reacts with ketones and aldehydes to yield δ -hydroxy-β-keto esters. These hydroxy esters can be dehydrated to the corresponding γ,δ-unsaturated-β-keto esters which are useful in annelation reactions to form cyclic β-keto esters. The dianion of methyl acetoacetate does not appear to undergo conjugate addition to simple α,β-unsaturated ketones, instead only carbonyl

  乙酰乙酸甲酯的二价阴离子与酮和醛反应生成δ-羟基-β-酮酯。这些羟基酯可以脱水为相应的 γ,δ-不饱和-β-酮酯，其可用于退火反应以形成环状 β-酮酯。乙酰乙酸甲酯的二价阴离子似乎不会与简单的 α,β-不饱和酮发生共轭加成，而只会发生羰基加成。
• 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。
• Peterson, John R.; Winter, Tamara J.; Miller, Chris P., Synthetic Communications, 1988, vol. 18, # 9, p. 949 - 964
  作者：Peterson, John R.、Winter, Tamara J.、Miller, Chris P.

  DOI：——

  日期：——
• Iodotrimethylsilane induced diastereoselective synthesis of tetrahydropyranones by a tandem Knoevenagel–Michael reaction
  作者：Gowravaram Sabitha、G.S.Kiran Kumar Reddy、M. Rajkumar、J.S. Yadav、K.V.S. Ramakrishna、A.C. Kunwar

  DOI：10.1016/j.tetlet.2003.08.020

  日期：2003.9

  The synthesis of multifunctionalized tetrahydropyranones has been achieved at room temperature with iodotrimethylsilane by a tandem Knoevenagel condensation of aldehydes with aldol adducts prepared from beta-keto esters and aldehydes, followed by a Michael reaction. The reactions are highly diastereoselective affording a single isomer in high yields. (C) 2003 Elsevier Ltd. All rights reserved.
• PETERSON, JOHN R.;WINTER, TAMARA J.;MILLER, CHRIS P., SYNTH. COMMUN., 18,(1988) N 9, 949-963
  作者：PETERSON, JOHN R.、WINTER, TAMARA J.、MILLER, CHRIS P.

  DOI：——

  日期：——