4-(1-羟基环己基)-2-重氮-3-氧代丁酸乙酯 | 259250-91-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-(1-羟基环己基)-2-重氮-3-氧代丁酸乙酯
• 英文名称: Ethyl 4-(1-hydroxycyclohexyl)-2-diazo-3-oxobutanoate
• 英文别名: ethyl 2-diazo-4-(1-hydroxycyclohexyl)-3-oxobutanoate；Ethyl 2-diazo-4-(1-hydroxycyclohexyl)-3-oxobutanoate
• CAS: 259250-91-4
• 化学式: C₁₂H₁₈N₂O₄
• 分子量: 254.286
• InChiKey: RBOWBGCGTBOKIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  65.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-(1-羟基环己基)-2-重氮-3-氧代丁酸乙酯 在 dirhodium tetraacetate 、 sodium hydroxide 、 硫酸 作用下， 以 甲苯 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：

  ethyl 4-(1-hydroxycyclohexyl)-3-oxobutanoate 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以68%的产率得到4-(1-羟基环己基)-2-重氮-3-氧代丁酸乙酯
  参考文献：
  名称：

  Rhodium(II)- and Copper(I)-Catalyzed Intramolecular Carbon-Hydrogen Bond Insertions with Metal Carbenoids Derived from Diazo Ketones

  摘要：

  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。

  DOI：

  10.1135/cccc19991807

文献信息

• 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。
• Synthesis of oxygen-containing heterocyclic compounds based on the intramolecular O–H insertion and Wolff rearrangement of α-diazocarbonyl compounds
  作者：Mingyi Liao、Suwei Dong、Guisheng Deng、Jianbo Wang

  DOI：10.1016/j.tetlet.2006.05.007

  日期：2006.7

  from β-keto α-diazo carbonyl compound to ketones or α,β-unsaturated compounds were subjected to Rh2(OAc)4-catalyzed and photo-induced diazo decomposition. The Rh2(OAc)4-catalyzed reaction afforded intramolecular O–H insertion products, while the photo-induced reaction gave Wolff rearrangement/intramolecular nucleophilic addition products. The transformations represent new approaches to tetrahydrofuran

  将由β-酮α-重氮羰基化合物衍生的钛（IV）-烯酸酯与酮或α，β-不饱和化合物的加成产物进行Rh 2（OAc）4催化和光诱导的重氮分解。Rh 2（OAc）4催化的反应提供了分子内O–H插入产物，而光诱导的反应产生了Wolff重排/分子内亲核加成产物。该转化代表了四氢呋喃和γ-丁内酯衍生物的新方法。
• A novel approach to bicyclic fused cyclopentenone derivatives
  作者：Guisheng Deng、Xue Tian、Jianbo Wang

  DOI：10.1016/s0040-4039(02)02579-0

  日期：2003.1

  A new four-step reaction sequence leading to bicyclic fused cyclopentenone derivatives starting from cyclic ketones has been developed.

  已开发出一种新的四步反应序列，该序列可从环酮开始生成双环稠合的环戊烯酮衍生物。
• A short protocol for the synthesis of spirocyclic tetrahydrofurans via intramolecular O–H insertion
  作者：Keith Jones、Teymour Toutounji

  DOI：10.1016/s0040-4020(01)00097-7

  日期：2001.3

  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.