t-butyl 2-chloro-2-methyl-3-oxo-3-phenylpropanoate | 1381800-74-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: t-butyl 2-chloro-2-methyl-3-oxo-3-phenylpropanoate
• 英文别名: tert-butyl (2S)-2-chloro-2-methyl-3-oxo-3-phenylpropanoate
• CAS: 1381800-74-3
• 化学式: C₁₄H₁₇ClO₃
• 分子量: 268.74
• InChiKey: IQBVRVDTJHEUEA-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  t-butyl 2-chloro-2-methyl-3-oxo-3-phenylpropanoate 、 苯酚 在 caesium carbonate 作用下， 以 甲苯 为溶剂， 以83%的产率得到t-butyl 2-methyl-3-oxo-2-phenoxy-3-phenylpropanoate
  参考文献：
  名称：

  在叔立体碳上用酚类合成威廉姆森醚：β-酮基酯的形式对映选择性苯氧基化

  摘要：

  首次描述了α-芳氧基-β-酮酸酯的对映选择性形成。路易斯酸催化β-酮酯的对映选择性氯化，随后与酚进行S N 2反应，生成ee高达96％的α-芳氧基-β-酮酯 。还发现α-氯-β-酮基酯的Favorskii重排产生1,2-二酯，其对映体纯度略有降低。

  DOI：

  10.1002/chem.201502042
• 作为产物：
  描述：

  tert-butyl 2-benzoylpropionate 在 N-氯代丁二酰亚胺 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 苯 为溶剂， 以78%的产率得到t-butyl 2-chloro-2-methyl-3-oxo-3-phenylpropanoate
  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

• Access to Both Enantiomers of α-Chloro-β-keto Esters with a Single Chiral Ligand: Highly Efficient Enantioselective Chlorination of Cyclic β-Keto Esters Catalyzed by Chiral Copper(II) and Zinc(II) Complexes of a Spiro-2,2′-bischroman-Based Bisoxazoline Li
  作者：Jie Li、Wei Pan、Zheng Wang、Xumu Zhang、Kuiling Ding

  DOI：10.1002/adsc.201200088

  日期：2012.7.9

  bisoxazoline ligands (SPANbox) were found to be highly efficient in copper(II)‐ and zinc(II)‐catalyzed asymmetric chlorinations of cyclic β‐keto esters with N‐chlorosuccinimide (NCS) as the chlorination reagent, to give the corresponding α‐chloro‐β‐keto esters in excellent yields in 5–30 min with ee values up to 97%. The copper(II) triflate and zinc(II) triflate complexes of a single SPANbox ligand demonstrated

  发现基于spiro-2,2'-双色原的手性双恶唑啉配体（SPANbox）在铜（II）和锌（II）催化的环状β-酮酯与N-氯代琥珀酰亚胺（NCS ）的不对称氯化反应中非常有效）作为氯化试剂，可在5-30分钟内以优异的收率得到相应的α-氯-β-酮酸酯，ee值高达97％。单个SPANbox配体的三氟甲磺酸铜（II）和三氟甲磺酸锌（II）配合物在对映体选择方面表现出彼此互补的结果，从而为氯化产物对映体的两种对映体提供了良好或优异的光学纯度。
• Williamson Ether Synthesis with Phenols at a Tertiary Stereogenic Carbon: Formal Enantioselective Phenoxylation of β‐Keto Esters
  作者：Kazutaka Shibatomi、Manato Kotozaki、Nozomi Sasaki、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1002/chem.201502042

  日期：2015.9.28

  The enantioselective formation of α‐aryloxy‐β‐keto esters is described for the first time. Lewis acid catalyzed enantioselective chlorination of β‐keto esters and subsequent SN2 reactions with phenols yielded α‐aryloxy‐β‐keto esters with up to 96 % ee. Favorskii rearrangement of α‐chloro‐β‐keto esters was also found to give 1,2‐diesters with slightly reduced enantiopurity.

  首次描述了α-芳氧基-β-酮酸酯的对映选择性形成。路易斯酸催化β-酮酯的对映选择性氯化，随后与酚进行S N 2反应，生成ee高达96％的α-芳氧基-β-酮酯 。还发现α-氯-β-酮基酯的Favorskii重排产生1,2-二酯，其对映体纯度略有降低。
• 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.