tert-butyl 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate | 142739-59-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: tert-butyl 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate
• 英文别名: tert-butyl 1-oxo-3,4-dihydro-2H-naphthalene-2-carboxylate
• CAS: 142739-59-1
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: LJGLTOHUZGVEJZ-UHFFFAOYSA-N

物化性质

• 沸点：
  350.5±31.0 °C(Predicted)
• 密度：
  1.119±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate 在 N-氯代丁二酰亚胺 、 C₃₅H₂₆N₂O₂ 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 苯 为溶剂， 以98%的产率得到tert-butyl (S)-2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate
  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：

  二碳酸二叔丁酯 在 4-二甲氨基吡啶 、 sodium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 tert-butyl 1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate
  参考文献：
  名称：

  β-酮基酯对MBH碳酸酯的有机催化对映选择性烯丙基烷基化†

  摘要：

  描述了由β-ICD催化的Morita-Baylis-Hillman碳酸盐与β-酮酸酯的高度立体选择性烯丙基烷基化。得到具有两个高的非对映选择性（高达10∶1dr）和对映选择性（高达95％ee）的高产率的含有两个相邻的季碳和叔碳中心的相应产物。

  DOI：

  10.1039/c4ob00682h

文献信息

• Organocatalytic Oxyamination of Azlactones: Kinetic Resolution of Oxaziridines and Asymmetric Synthesis of Oxazolin-4-ones
  作者：Shunxi Dong、Xiaohua Liu、Yin Zhu、Peng He、Lili Lin、Xiaoming Feng

  DOI：10.1021/ja404379n

  日期：2013.7.10

  example of oxyamination of azlactones with oxaziridines was realized using a chiral bisguanidinium salt. Efficient catalytic asymmetric oxyamination and kinetic resolution of oxaziridines occurred simultaneously. Various chiral oxazolin-4-one derivatives with potential biological activity were obtained (up to 92% ee). Meanwhile, a series of optically pure oxaziridines were recovered with up to 99% ee and

  使用手性双胍盐实现吖内酯与恶氮丙啶氧胺化的第一个实例。氧氮丙啶的高效催化不对称氧化胺化和动力学拆分同时发生。获得了具有潜在生物活性的各种手性 oxazolin-4-one 衍生物（高达 92% ee）。同时，回收了一系列光学纯氧氮杂环丙烷，ee 高达 99%，并成功用于 3-甲基-1H-吲哚和苯乙烯的不对称氧化胺化。还通过对照实验研究了三重立体分化过程。
• Organocatalytic Asymmetric Conjugate Addition to Allenic Esters and Ketones
  作者：Petteri Elsner、Luca Bernardi、Giorgio Dela Salla、Jacob Overgaard、Karl Anker Jørgensen

  DOI：10.1021/ja710689c

  日期：2008.4.1

  having different ring sizes, ring systems, and substituents in high yields and enantioselectivities. Glycine imine derivatives also undergo the asymmetric conjugate addition to electron-deficient allenes in high yields and with enantioselectivities in the range of 60-88% ee, thus providing a rapid entry to optically active alpha-vinyl-substituted alpha-amino acid derivatives. It is shown that the enantioselectivity

  描述了环状β-酮酯和甘氨酸亚胺衍生物与缺电子丙二烯的有机催化对映选择性共轭加成的第一个例子。我们公开了相应的手性 β，γ-不饱和羰基化合物仅在相转移条件下使用金鸡纳生物碱衍生或联苯基手性季铵盐作为催化剂形成。β-酮酯的反应范围概述了具有酮或酯基序作为吸电子基团的丙二烯以及在 3 位具有不同取代基的丙二烯，从而以高产率和优异的非对映选择性和对映选择性得到旋光产物（ 90-96% ee)。对于许多具有不同环大小、环系统、和高产率和对映选择性的取代基。甘氨酸亚胺衍生物还以高产率与缺电子丙二烯进行不对称共轭加成，对映选择性在 60-88% ee 范围内，从而快速进入光学活性 α-乙烯基取代的 α-氨基酸衍生物。结果表明，对映选择性强烈依赖于亲核试剂的酯部分与所用催化体系的结合。这些新的催化过程产生的手性产物的高合成价值通过两种直接的转化得到证明，一种是光学活性的六氢苯并吡喃酮，另一种是取代的焦谷氨
• Catalytic asymmetric cross-dehydrogenative coupling: activation of C–H bonds by a cooperative bimetallic catalyst system
  作者：Weidi Cao、Xiaohua Liu、Ruixue Peng、Peng He、Lili Lin、Xiaoming Feng

  DOI：10.1039/c3cc41315b

  日期：——

  A cooperative bimetallic catalyst system was applied in the catalytic asymmetric cross-dehydrogenative coupling of β-ketoesters and xanthene. Various optically active xanthene derivatives bearing a quaternary stereogenic carbon center were obtained in moderate to good yields (up to 90%) with excellent enantioselectivities (up to 99% ee). Meanwhile, a transition-state model was proposed to explain the origin of the asymmetric induction.

  一种双金属协同催化体系被应用于β-酮酯与咕吨的催化不对称交叉脱氢偶联反应中。以中等至良好的产率（高达90%）合成了多种带有季碳立体中心的手性咕吨衍生物，且具有极佳的对映选择性（高达99% ee）。同时，提出了一种过渡态模型，以解释不对称诱导的起源。
• <i>N</i>-Trifluoromethylthiophthalimide: A Stable Electrophilic SCF₃-Reagent and its Application in the Catalytic Asymmetric Trifluoromethylsulfenylation
  作者：Teerawut Bootwicha、Xiangqian Liu、Roman Pluta、Iuliana Atodiresei、Magnus Rueping

  DOI：10.1002/anie.201304957

  日期：2013.12.2

  Cinchona alkaloid catalysts in combination with air‐ and moisture‐stable N‐trifluoromethylthiophthalimide as electrophilic SCF3 source enabled the catalytic enantioselective trifluoromethylsulfenylation. Thus, a series of α‐SCF3 esters that bear a quaternary carbon stereogenic center were obtained with excellent yield and enantioselectivity. Moreover, the products can be readily converted into valuable

  金鸡纳生物碱催化剂与空气和湿气稳定的N-三氟甲基硫代邻苯二甲酰亚胺作为亲电子SCF 3来源，可实现催化对映选择性的三氟甲基亚磺酰化。因此，一系列α-SCF的3均具有优异的产率和对映选择性得到酯而承受的季碳立体中心。此外，该产品可容易地转化成有价值的α-SCF 3 β羟基酯。
• Synthesis, Characterization, and Reactivity of a Hypervalent‐Iodine‐Based Nitrooxylating Reagent
  作者：Roxan Calvo、Antoine Le Tellier、Thomas Nauser、David Rombach、Darryl Nater、Dmitry Katayev

  DOI：10.1002/anie.202005720

  日期：2020.9.21

  synthesis and characterization of a hypervalent‐iodine‐based reagent that enables a direct and selective nitrooxylation of enolizable C−H bonds to access a broad array of organic nitrate esters is reported. This compound is bench stable, easy‐to‐handle, and delivers the nitrooxy (‐ONO2) group under mild reaction conditions. Activation of the reagent by Brønsted and Lewis acids was demonstrated in the synthesis

  本文报道了一种基于高价碘的试剂的合成和表征，该试剂能够使可烯醇化的CH键进行直接和选择性的硝基氧化，从而获得广泛的有机硝酸酯。该化合物在工作台上稳定，易于处理，并能释放出硝基氧基（-ONO 2）组在温和的反应条件下。在硝基氧化的β-酮酸酯，1,3-二酮和丙二酸酯的合成中证明了Brønsted和Lewis酸对试剂的激活，而在硝基氧化的吲哚的合成中则显示了其在光氧化还原催化下的活性。详细的机理研究包括脉冲辐解，斯特恩-沃尔默淬灭研究和UV / Vis光谱电化学，揭示了一种独特的单电子转移（SET）诱导的协同机理，与硝酸根自由基的产生无关。