3,3-bis(methoxycarbonyl)-6-oxoheptanoic acid | 1262290-33-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,3-bis(methoxycarbonyl)-6-oxoheptanoic acid
• CAS: 1262290-33-4
• 化学式: C₁₁H₁₆O₇
• 分子量: 260.244
• InChiKey: WGFSPFYZPHREDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,3-bis(methoxycarbonyl)-6-oxoheptanoic acid 在 水 、 sodium chloride 作用下， 以 二甲基亚砜 为溶剂， 反应 0.5h， 以34%的产率得到3-(methoxycarbonyl)-6-oxoheptanoic acid
  参考文献：
  名称：

  A Diastereoselective, Nucleophile-Promoted Aldol-Lactonization of Ketoacids Leading to Bicyclic-β-Lactones

  摘要：

  An improved, tandem acid activation/aldol-lactonization process is described. This more practical protocol shortens reaction times for the construction of bicyclic beta-lactones from ketoacids and implements the use of commercially available reagents p-toluenesulfonyl chloride (p-TsC1) as activator and 4-dimethylaminopyridine (4-DMAP) as nucleophllic promoter (Lewis base). Substrates with beta-substituents, with respect to the carboxylic acid, consistently showed excellent levels of diastereoselectivity during the bis-cyclization event.

  DOI：

  10.1021/jo202252y
• 作为产物：
  描述：

  1-benzyl 2,2-dimethyl 5-oxohexane-1,2,2-tricarboxylate 在 5% palladium on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以1.3 g的产率得到3,3-bis(methoxycarbonyl)-6-oxoheptanoic acid
  参考文献：
  名称：

  用酮酸对映选择性，有机催化的分子内羟醛缩醛化反应，导致双环和三环β-内酯的形成和拓扑构型转变

  摘要：

  迅速出现的复杂性表征了具有酮酸底物和随后的拓扑改变反应的不对称，亲核催化的醛醇内酯化（NCAL）过程。证明了手性环状异硫脲催化剂作为亲核助催化剂（刘易斯碱）可通过可扩展的NCAL工艺进行脱对称反应的用途（参见图片； HBTM =同苯并四甲醚）。

  DOI：

  10.1002/anie.201004671

文献信息

• Enantioselective Synthesis of Functionalized β-Lactones by NHC-Catalyzed Aldol Lactonization of Ketoacids
  作者：Santigopal Mondal、Subrata Mukherjee、Tamal Kanti Das、Rajesh G. Gonnade、Akkattu T. Biju

  DOI：10.1021/acs.joc.7b01526

  日期：2017.9.1

  leading to the enantioselective synthesis of cyclopentane-fused β-lactones is presented. The reaction proceeds via the generation of NHC-bound enolate intermediates formed from the ketoacids in the presence of the peptide coupling reagent HATU and NHC generated from the chiral triazolium salt. The functionalized β-lactones are formed under mild conditions in high yields and enantioselectivities.

  提出了N-杂环卡宾（NHC）催化的分子内羟醛缩醛内酯的易得的酮酸的内酯化作用，从而导致环戊烷稠合的β-内酯的对映选择性合成。该反应通过在由手性三唑鎓盐产生的肽偶联剂HATU和NHC的存在下由酮酸形成的与NHC结合的烯醇酸酯中间体的进行而进行。功能化的β-内酯在温和条件下以高收率和对映选择性形成。
• Enantioselective, Organocatalyzed, Intramolecular Aldol Lactonizations with Keto Acids Leading to Bi- and Tricyclic β-Lactones and Topology-Morphing Transformations
  作者：Carolyn A. Leverett、Vikram C. Purohit、Daniel Romo

  DOI：10.1002/anie.201004671

  日期：2010.12.3

  Quickly emerging complexity characterizes the asymmetric, nucleophile‐catalyzed aldol lactonization (NCAL) process with keto acid substrates and subsequent topology‐altering reactions. The utility of chiral cyclic isothiourea catalysts as nucleophilic promoters (Lewis bases) for desymmetrization reactions through scaleable NCAL processes is demonstrated (see picture; HBTM=homobenzotetramisole).

  迅速出现的复杂性表征了具有酮酸底物和随后的拓扑改变反应的不对称，亲核催化的醛醇内酯化（NCAL）过程。证明了手性环状异硫脲催化剂作为亲核助催化剂（刘易斯碱）可通过可扩展的NCAL工艺进行脱对称反应的用途（参见图片； HBTM =同苯并四甲醚）。
• A Diastereoselective, Nucleophile-Promoted Aldol-Lactonization of Ketoacids Leading to Bicyclic-β-Lactones
  作者：Gang Liu、Morgan E. Shirley、Daniel Romo

  DOI：10.1021/jo202252y

  日期：2012.3.2

  An improved, tandem acid activation/aldol-lactonization process is described. This more practical protocol shortens reaction times for the construction of bicyclic beta-lactones from ketoacids and implements the use of commercially available reagents p-toluenesulfonyl chloride (p-TsC1) as activator and 4-dimethylaminopyridine (4-DMAP) as nucleophllic promoter (Lewis base). Substrates with beta-substituents, with respect to the carboxylic acid, consistently showed excellent levels of diastereoselectivity during the bis-cyclization event.