2-pivaloylcycloheptanone | 61363-32-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-pivaloylcycloheptanone
• 英文别名: tert-butyl 2-oxocycloheptane-1-carboxylate；tert-Butyl 2-oxocycloheptane-1-carboxylate
• CAS: 61363-32-4
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: BSTPLHQNXRIIRH-UHFFFAOYSA-N

物化性质

• 沸点：
  290.9±33.0 °C(Predicted)
• 密度：
  1.021±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2-pivaloylcycloheptanone 在 N-氯代丁二酰亚胺 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 苯 为溶剂， 以92%的产率得到t-butyl 1-chloro-2-oxocycloheptanecarboxylate
  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 、 环庚酮 在 sodium hydride 作用下， 生成 2-pivaloylcycloheptanone
  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

• The Amino Thiourea-Catalyzed Asymmetric Nucleophilic Reactions
  作者：Yoshiji Takemoto、Hideto Miyabe

  DOI：10.2533/chimia.2007.269

  日期：——

  Bifunctional amino thiourea-catalyzed asymmetric additions of several nucleophiles into electron-deficient unsaturated compounds such as nitroolefins, ?,?-unsaturated imides, imines, and azodicarboxylates are described. We discovered that bifunctional thioureas bearing a tertiary amino group significantly accelerated several nucleophilic addition reactions of active methylene compounds to electron-deficient double bonds. In these reactions, a strong hydrogen-bonding ability of the thiourea moiety as well as an appropriate Brønsted basicity of the tertiary amine is crucial for high enantioselectivity. This dual activation of both nucleophiles and electrophiles by the bifunctional thiourea expanded the applicability of the thiourea-catalyzed enantioselective reaction. In addition, these organocatalyzed asymmetric reactions were successfully applied to the concise asymmetric synthesis of natural products and medicinal candidates such as epibatidine, baclofen, and CP-99,994.

  双功能氨基硫脲催化的不对称加成反应将几种亲核试剂加入到电子不足的不饱和化合物中，如硝基烯烃、α，β-不饱和亚酰胺、亚胺和叠氮二羧酸酯。我们发现，含有三级胺基的双功能硫脲显著加速了活性亚甲基化合物与电子不足双键的几种亲核加成反应。在这些反应中，硫脲基团的强氢键能力以及三级胺的适当Brønsted碱性对高对映选择性至关重要。双功能硫脲对亲核试剂和电子亲电试剂的双重活化扩展了硫脲催化的不对称反应的适用范围。此外，这些有机催化的不对称反应成功应用于天然产物和药用候选化合物的简洁不对称合成，如蛙毒碱、氯硝西泮和CP-99,994。
• Organocatalytic Enantioselective Hydrazination of 1,3-Dicarbonyl ­Compounds: Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids
  作者：Yoshiji Takemoto、Xuenong Xu、Takaya Yabuta、Pei Yuan

  DOI：10.1055/s-2005-922766

  日期：——

  The organocatalytic α-hydrazination of β-keto esters using a bifunctional urea as catalyst and azodicarboxylates as electrophiles has been investigated and is shown to proceed in high yields and with good enantioselectivity. The scope of the reaction is demonstrated for various substrates and the urea catalyst 1b was revealed to be superior to thiourea la. Furthermore, transformation of the obtained

  已经研究了使用双功能尿素作为催化剂和偶氮二羧酸盐作为亲电试剂的 β-酮酯的有机催化 α-肼化反应，并显示出高产率和良好的对映选择性。对各种底物证明了反应范围，并且显示尿素催化剂1b优于硫脲1a。此外，还介绍了所得产物4aa向旋光氨基酸衍生物10的转化。
• Zinc-catalyzed Enantioselective Electrophilic Amination of β-Ketocarbonyl Compounds with Axially Chiral Phenanthroline Ligands
  作者：Yuki Naganawa、Hiroyuki Komatsu、Hisao Nishiyama

  DOI：10.1246/cl.150802

  日期：2015.12.5

  Zinc-catalyzed asymmetric α-amination of β-ketocarbonyl compounds 2 using dialkyl azodicarboxylates 3 as the electrophilic nitrogen source is described. The complexes of Zn(OTf)2 and the axially ch...

  描述了使用偶氮二羧酸二烷基酯 3 作为亲电子氮源的 β-酮羰基化合物 2 的锌催化不对称 α-胺化。Zn(OTf)2 与轴向腐蚀的配合物...
• Catalyst-Free Decarboxylative Fluorination of Tertiary β-Keto Carboxylic Acids
  作者：Kazutaka Shibatomi、Misaki Katada、Kazumasa Kitahara、Seiji Iwasa

  DOI：10.1055/s-0037-1611019

  日期：2018.11

  Decarboxylative fluorination of tertiary β-keto carboxylic ­acids was performed using an electrophilic fluorinating reagent. The reaction proceeded in the absence of a catalyst or base to yield the corresponding α-fluoroketones with tertiary fluorocarbons in good to high yields. Considering that the α-fluorination of asymmetrical ketones ­often causes problems with the regioselectivity between the

  使用亲电子氟化试剂进行叔 β-酮羧酸的脱羧氟化。该反应在不存在催化剂或碱的情况下进行，以良好至高产率产生相应的α-氟代酮和叔碳氟化合物。考虑到不对称酮的 α-氟化通常会导致 α-和 α'-位之间的区域选择性问题，该方法可能是合成叔氟酮的简单酮的 α-氟化的良好替代方法。
• Direct catalytic asymmetric aldol reaction of β-keto esters with formaldehyde promoted by a dinuclear Ni2-Schiff base complex
  作者：Shinsuke Mouri、Zhihua Chen、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1039/b912380f

  日期：——

  A homodinuclear Ni(2)-Schiff base 1 complex (0.1-1 mol%) promoted the direct catalytic asymmetric aldol reaction of beta-keto esters with formaldehyde, giving hydroxymethylated adducts in 94-66% ee.

  均核Ni（2）-席夫碱1配合物（0.1-1 mol％）促进了β-酮酯与甲醛的直接催化不对称醛醇缩合反应，得到94-66％ee的羟甲基化加合物。