tert-butyl (S)-1-chloro-2-oxocyclopentanecarboxylate | 724762-42-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl (S)-1-chloro-2-oxocyclopentanecarboxylate
• 英文别名: t-butyl 1-chloro-2-oxocyclopentanecarboxylate；tert-butyl (1S)-1-chloro-2-oxocyclopentane-1-carboxylate
• CAS: 724762-42-9
• 化学式: C₁₀H₁₅ClO₃
• 分子量: 218.68
• InChiKey: NOAGIHODUZZBCB-JTQLQIEISA-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

• 作为反应物：
  描述：

  tert-butyl (S)-1-chloro-2-oxocyclopentanecarboxylate 在 sodium azide 、 10 % Pd-BaSO4 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 反应 1.0h， 生成 t-butyl 1-amino-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
• 作为产物：
  描述：

  1-吡咯甲酸叔丁酯 在 N-氯代丁二酰亚胺 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 、 sodium hydride 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 tert-butyl (S)-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

• Cu(I)-catalyzed asymmetric chlorination of β-keto esters in the presence of chiral phosphine-schiff base type ligands
  作者：Jia-Jun Jiang、Jian Huang、De Wang、Zhi-Liang Yuan、Mei-Xin Zhao、Fei-Jun Wang、Min Shi

  DOI：10.1002/chir.20913

  日期：2011.3

  Chiral phosphine‐Schiff base type ligand L8 prepared from (R)‐(−)‐2‐(diphenylphosphino)‐1,1'‐binaphthyl‐2'‐amine was found to be a fairly effective ligand for Cu(I)‐promoted enantioselective chlorination of β‐keto esters to give the corresponding products in high yields and with moderate enantioselectivities. Chirality 2011. © 2010 Wiley‐Liss, Inc.

  由（R）-（-）-2-（二苯基膦基）-1,1'-联萘-2-'胺制备的手性膦Schiff碱型配体L8被发现是Cu（I）促进的相当有效的配体β-酮酯的对映选择性氯化，以高收率和中等对映选择性得到相应的产物。手性2011。©2010 Wiley-Liss，Inc.。
• 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。
• Catalytic enantioselective chlorination of cyclic β-keto esters in the presence of chiral Pd(II) complexes
  作者：Young Ku Kang、Hee Hun Kim、Kwang Oh Koh、Dae Young Kim

  DOI：10.1016/j.tetlet.2012.05.064

  日期：2012.7

  The catalytic enantioselective electrophilic chlorination promoted by chiral palladium complexes is described. The treatment of β-keto esters with 2,3,4,5,6,6-hexachlorocyclohex-2,4-dienone as chlorine source under mild reaction conditions afforded the corresponding α-chlorinated β-keto esters with excellent enantioselectivities (up to 94% ee).

  描述了由手性钯配合物促进的催化对映选择性亲电子氯化。在温和的反应条件下，用2,3,4,5,6,6-六氯环己基-2,4-二烯酮作为氯源处理β-酮酯，得到相应的α-氯代β-酮酯，其对映选择性极好（最高可达94％ee）。
• 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
  作者：Kazutaka Shibatomi、Yoshinori Soga、Akira Narayama、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1021/ja304806j

  日期：2012.6.20

  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.