N-(methoxycarbonyl)-4-(tert-butoxycarbonyl)-4-hydroxy-3-pyrrolidinone | 1180519-45-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: N-(methoxycarbonyl)-4-(tert-butoxycarbonyl)-4-hydroxy-3-pyrrolidinone
• 英文别名: 3-O-tert-butyl 1-O-methyl (3S)-3-hydroxy-4-oxopyrrolidine-1,3-dicarboxylate
• CAS: 1180519-45-2
• 化学式: C₁₁H₁₇NO₆
• 分子量: 259.259
• InChiKey: BFSQXYADNRWLHP-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  93.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  N-(methoxycarbonyl)-4-(tert-butoxycarbonyl)-3-pyrrolidinone 在 [(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]-diaquo-palladium(II) bis(triflate) 、 二甲基二环氧乙烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以38%的产率得到N-(methoxycarbonyl)-4-(tert-butoxycarbonyl)-4-hydroxy-3-pyrrolidinone
  参考文献：
  名称：

  Palladium-catalysed enantioselective α-hydroxylation of β-ketoesters

  摘要：

  使用双阳离子钯(II) 催化剂和二甲基二氧杂环己烷作为氧化剂，可以实现环状和无环1,3-酮酯的高度对映选择性α-羟基化，EE 高达 98%。

  DOI：

  10.1039/b907151b

文献信息

• Delineating Origins of Stereocontrol in Asymmetric Pd-Catalyzed α-Hydroxylation of 1,3-Ketoesters
  作者：Alexander M. R. Smith、Henry S. Rzepa、Andrew J. P. White、Denis Billen、King Kuok (Mimi) Hii

  DOI：10.1021/jo1002906

  日期：2010.5.7

  Systematic studies of reaction conditions and subsequent optimization led to the identification of important parameters for stereoselectivity in the asymmetric alpha-hydroxylation reaction of 1,3-ketoesters. Enantioselectivities of up to 98% can be achieved for cyclic substrates and 88% for acyclic ketoesters. Subsequently, the combination of cyclic/acyclic ketoester, catalyst, and oxidant was found to have a profound effect on reaction rates and turnover-limiting steps. The stereochemistry of the reaction contradicts that observed for other similar electrophilic substitution reactions. This was rationalized by transition-state modeling, which revealed a number of cooperative weak interactions between oxidant, ligand, and counterion, together with C-H/pi interactions that cumulatively account for the unusual stereoselectivity.