ethyl 2-oxooctahydroindeno-[7a,1-b]oxen-4a-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: ethyl 2-oxooctahydroindeno-[7a,1-b]oxen-4a-carboxylate
• 英文别名: ethyl (2aR,4aS,8aR)-2-oxo-3,4,5,6,7,8-hexahydro-2aH-indeno[7a,1-b]oxete-4a-carboxylate
• 化学式: C₁₃H₁₈O₄
• 分子量: 238.284
• InChiKey: RSQYIXBCBGEZGH-ZWKOPEQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2-oxooctahydroindeno-[7a,1-b]oxen-4a-carboxylate 、 重氮乙酸乙酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以57%的产率得到ethyl (1SR,3aRS,7aSR)-1-(2-diazo-3-ethoxy-3-oxopropanoyl)-7a-hydroxyoctahydroindene-3a-carboxylate
  参考文献：
  名称：

  稠合双环和三环β-内酯通过扩环和OH插入转化为融合γ-内酯和3（2 H）-呋喃酮

  摘要：

  研究了一种将β-内酯转化为γ-内酯和3（2 H）-呋喃酮的两步策略，涉及初始的酰基C-O裂解，产生δ-羟基-α-重氮-β-酮酸酯和β-酮膦酸酯。这些α-重氮中间体的随后串联Wolff重排/内酯化在光解或热解条件下有效地提供了顺式融合的γ-内酯。此外，通过铑（II）催化δ-羟基-α-重氮中间体的OH插入反应，获得了顺式稠合的3（2 H）-呋喃酮。

  DOI：

  10.1021/jo7012934
• 作为产物：
  描述：

  1-(3-Carboxy-propyl)-2-oxo-cyclohexanecarboxylic acid ethyl ester 在 2-bromo-N-propylpyridinium triflate 、 4-吡咯烷基吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以70%的产率得到ethyl 2-oxooctahydroindeno-[7a,1-b]oxen-4a-carboxylate
  参考文献：
  名称：

  Bicyclic- and Tricyclic-β-lactones via Organonucleophile-Promoted Bis-Cyclizations of Keto Acids:  Enantioselective Synthesis of (+)-Dihydroplakevulin

  摘要：

  A highly diastereoselective, nucleophile-promoted bis-cyclization process, employing readily available and tractable keto acid substrates, is described. This methodology provides concise access to bicyclic- and tricyclic-beta-lactones bearing tertiary carbinol centers and quaternary carbons, greatly extending the scope of previous routes to bicyclic-beta-lactones from aldehyde acid substrates. The utility of the method was demonstrated by application to an enantioselective synthesis of (+)-dihydroplakevulin A. This and related processes may be revealing a subtle interplay between [2+2] cycloaddition and nucleophile-catalyzed aldol lactonization (NCAL) reaction manifolds.

  DOI：

  10.1021/ol061816t

文献信息

• Conjugate reduction and reductive aldol cyclization of α,β-unsaturated thioesters catalyzed by (BDP)CuH
  作者：Ninglin Li、Jun Ou、Michel Miesch、Pauline Chiu

  DOI：10.1039/c1ob05352c

  日期：——

  A conjugate reduction of α,β-unsaturated thioesters catalyzed by copper hydride using PMHS as stoichiometric reductant has been developed. 1,2-Bis(diphenylphosphino)benzene (BDP) was the most effective ligand for this reduction. Saturated thioesters could be produced in excellent yields when the substituent on the thiol is not sterically-demanding. This protocol was applied to induce the reductive aldol cyclization of keto-enethioates, which could offer β-hydroxythioesters in moderate to good yields.

  已开发出一种由铜氢化物催化、使用PMHS作为化学计量还原剂的α,β-不饱和硫酯的共轭还原反应。1,2-双(二苯膦基)苯（BDP）是该还原反应最有效的配体。当硫醇上的取代基空间要求不高时，可以高产率地生成饱和硫酯。该方案被应用于诱导酮烯硫酯的还原性醛醇环化反应，从而在中等至良好产率下获得β-羟基硫酯。
• Transformation of Fused Bicyclic and Tricyclic β-Lactones to Fused γ-Lactones and 3(2<i>H</i>)-Furanones via Ring Expansions and O−H Insertions
  作者：Wei Zhang、Daniel Romo

  DOI：10.1021/jo7012934

  日期：2007.11.1

  of β-lactones to γ-lactones and 3(2H)-furanones was developed involving initial acyl C−O cleavage leading to δ-hydroxy-α-diazo-β-ketoesters and β-ketophosphonates. Subsequent tandem Wolff rearrangement/lactonization of these α-diazo intermediates provided cis-fused γ-lactones efficiently under photolytic or thermolytic conditions. In addition, cis-fused 3(2H)-furanones were obtained by rhodium(II)-catalyzed

  研究了一种将β-内酯转化为γ-内酯和3（2 H）-呋喃酮的两步策略，涉及初始的酰基C-O裂解，产生δ-羟基-α-重氮-β-酮酸酯和β-酮膦酸酯。这些α-重氮中间体的随后串联Wolff重排/内酯化在光解或热解条件下有效地提供了顺式融合的γ-内酯。此外，通过铑（II）催化δ-羟基-α-重氮中间体的OH插入反应，获得了顺式稠合的3（2 H）-呋喃酮。
• Bicyclic- and Tricyclic-β-lactones via Organonucleophile-Promoted Bis-Cyclizations of Keto Acids:  Enantioselective Synthesis of (+)-Dihydroplakevulin
  作者：Huda Henry-Riyad、Changsuk Lee、Vikram C. Purohit、Daniel Romo

  DOI：10.1021/ol061816t

  日期：2006.9

  A highly diastereoselective, nucleophile-promoted bis-cyclization process, employing readily available and tractable keto acid substrates, is described. This methodology provides concise access to bicyclic- and tricyclic-beta-lactones bearing tertiary carbinol centers and quaternary carbons, greatly extending the scope of previous routes to bicyclic-beta-lactones from aldehyde acid substrates. The utility of the method was demonstrated by application to an enantioselective synthesis of (+)-dihydroplakevulin A. This and related processes may be revealing a subtle interplay between [2+2] cycloaddition and nucleophile-catalyzed aldol lactonization (NCAL) reaction manifolds.