tert-butyl (R)-1-chloro-2-oxocyclopentanecarboxylate | 1224588-49-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl (R)-1-chloro-2-oxocyclopentanecarboxylate
• 英文别名: t-butyl 1-chloro-2-oxocyclopentanecarboxylate；tert-butyl (1R)-1-chloro-2-oxocyclopentane-1-carboxylate
• CAS: 1224588-49-1
• 化学式: C₁₀H₁₅ClO₃
• 分子量: 218.68
• InChiKey: NOAGIHODUZZBCB-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-吡咯甲酸叔丁酯 在 N-氯代丁二酰亚胺 、 (R)-Spymox 、 copper(II) bis(trifluoromethanesulfonate) 、 sodium hydride 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 tert-butyl (R)-1-chloro-2-oxocyclopentanecarboxylate
  参考文献：
  名称：

  Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers

  摘要：

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.

  DOI：

  10.1021/ja304806j

文献信息

• Chiral 2-Amino Alcohol Derivatives Catalyze the Enantioselective α-Chlorination of β-Ketoesters
  作者：Baohua Zhang、Ruixia Guo、Sijie Liu、Lanxiang Shi、Xiaoyun Li

  DOI：10.5012/bkcs.2014.35.6.1759

  日期：2014.6.20

  The enantioselective $\alpha}$-chlorination of cyclic $\beta}$-ketoesters catalyzed by chiral 2-aminoalcohol derivatives (2f) has been developed. For the optically active $\alpha}$-chlorinated products, the isolated yields are in the range of 85-94% and the enantiomeric excesses are up to 84% ee.

  在手性 2-氨基甲醇衍生物 (2f) 的催化下，开发了环状 $\α}$ 酮酯的对映选择性 $\β}$ 氯化反应。对于具有光学活性的$\alpha}$氯化产物，分离产率在 85-94% 之间，对映体过量率高达 84% ee。
• Asymmetric Chlorination of Cyclic β-Keto Esters and N-Boc Oxindoles­ Catalyzed by an Iron(III)-BPsalan Complex
  作者：Zhen-Jiang Xu、Chi-Ming Che、Yong-Heng Luo、Yuan-Ji Ping、Zong-Rui Li、Xin Gu

  DOI：10.1055/s-0036-1590955

  日期：2018.3

  Abstract An iron(III)-BPsalan complex was found to efficiently catalyze the asymmetric chlorination reaction of cyclic β-keto esters and N-Boc oxindoles, affording the corresponding chlorinated products in high yield and up to 92% ee with NCS as chlorination reagent under mild reaction conditions. An iron(III)-BPsalan complex was found to efficiently catalyze the asymmetric chlorination reaction of

  摘要 发现铁（III）-BPsalan络合物可有效催化环状β-酮酯和N - Boc羟吲哚的不对称氯化反应，在温和的条件下以NCS作为氯化试剂，可提供高产率和高达92％ee的相应氯化产物。反应条件。 发现铁（III）-BPsalan络合物可有效催化环状β-酮酯和N - Boc羟吲哚的不对称氯化反应，在温和的条件下以NCS作为氯化试剂，可提供高产率和高达92％ee的相应氯化产物。反应条件。