methyl 4-methylindanone-2-carboxylate | 91963-24-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: methyl 4-methylindanone-2-carboxylate
• 英文别名: 2-Methoxycarbonyl-4-methylindan-1-on；2-Carbomethoxy-4-methyl-hydrindon；Methyl 4-methyl-1-oxo-2-indanecarboxylate；methyl 7-methyl-3-oxo-1,2-dihydroindene-2-carboxylate
• CAS: 91963-24-5
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: ANAXUBZSZJVHPT-UHFFFAOYSA-N

物化性质

• 沸点：
  329.0±31.0 °C(Predicted)
• 密度：
  1.209±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  methyl 4-methylindanone-2-carboxylate 在 氢氧化钾 、 sodium methylate 作用下， 反应 43.5h， 生成 4,7'-Dimethyl-2,2'-spirobiindan-1,1'-dion
  参考文献：
  名称：

  Aromatische Spirane, 23. Mitt.: Darstellung von unsymmetrisch substituierten Dimethyl-2,2?-Spirobiindan-1,1?-dionen

  摘要：

  Both spirodiketones 7 and 8 were obtained as a mixture (56:44) by treatment of dicarbonic acid 5 with polyphosphoric acid (PPA). 5 was accessible from dimethylester 3, synthesized by retro-Claisen reaction between 1 and 2. In the same way, 30 was obtained via 27. The preparation of the pure spiro compounds 7 and 8, resp., was achieved by aldol reaction between 9 and 10 or 9 and 16, resp. Short treatment of the resulting compounds 11 and 17 with diazomethane yielded the methylbenzoates 12 and 18. Prolonged reaction (several hours) gave the pyrazole compounds 14 and 19, resp., which were also obtained (several days) from phthalides 14 and 20. The latter were formed from the benzylidene compounds 11 and 17, resp., by heating. 11 and 17 (after hydrogenation to 15a and 21a) were cyclized either with PPA or thermically to the spiro compounds 7 and 8. The main product 20 was cyclized thermically to 8 after reduction with zinc to a mixture of 21a and 8 (20:75).

  DOI：

  10.1007/bf00810885
• 作为产物：
  描述：

  4-甲基-1-茚酮 、 碳酸二甲酯 反应 1.0h， 生成 methyl 4-methylindanone-2-carboxylate
  参考文献：
  名称：

  β-酮酯和β-酮酰胺的手性N，N'-二氧化物有机催化的不对称亲电α-氰化

  摘要：

  使用高价碘作为氰化物转移剂，实现了1-茚满酮衍生的β-酮酯和β-酮酰胺的对映选择性亲电子α-氰化反应。在无机碱存在下，手性N，N'-二氧化物被用作有效的双官能有机催化剂，它以50-99％的产率提供了相应的α-氰基二羰基化合物，具有良好的对映选择性（87-97％ee）。

  DOI：

  10.1021/acs.joc.6b02726

文献信息

• Organocatalytic Michael Addition of 1,3-Dicarbonyl Indane Compounds to Nitrostyrenes
  作者：Zhen-Yu Jiang、Hua-Meng Yang、Ya-Dong Ju、Li Li、Meng-Xian Luo、Guo-Qiao Lai、Jian-Xiong Jiang、Li-Wen Xu

  DOI：10.3390/molecules15042551

  日期：——

  To map out the efficient organocatalyst requirements in the Michael addition of 1,3-dicarbonyl indane compounds to nitrostyrenes, a dozen different amino organocatalysts containing a p-toluenesulfonyl group (Ts) have been evaluated; excellent enantio-selectivities (up to er 92:8) were obtained with a primary amine-based Ts-DPEN catalyst and a plausible catalytic reaction mechanism was proposed on the

  为了确定将 1,3-二羰基茚满化合物迈克尔加成到硝基苯乙烯中的有效有机催化剂要求，对十几种含有对甲苯磺酰基 (Ts) 的不同氨基有机催化剂进行了评估；使用伯胺基 Ts-DPEN 催化剂获得了优异的对映选择性（高达 92:8），并根据实验结果提出了合理的催化反应机理。
• Chiral <i>N</i>,<i>N</i>′-Dioxide Organocatalyzed Asymmetric Electrophilic α-Cyanation of β-Keto Esters and β-Keto Amides
  作者：Baiwei Ma、Xiaobin Lin、Lili Lin、Xiaoming Feng、Xiaohua Liu

  DOI：10.1021/acs.joc.6b02726

  日期：2017.1.6

  An enantioselective electrophilic α-cyanation of 1-indanone-derived β-keto esters and β-keto amides using a hypervalent iodine as the cyanide-transfer reagent was realized. A chiral N,N′-dioxide was used as the efficient bifunctional organocatalyst in the presence of inorganic base, which gave the corresponding α-cyano dicarbonyl compounds in yields of 50–99% with good enantioselectivities (87–97%

  使用高价碘作为氰化物转移剂，实现了1-茚满酮衍生的β-酮酯和β-酮酰胺的对映选择性亲电子α-氰化反应。在无机碱存在下，手性N，N'-二氧化物被用作有效的双官能有机催化剂，它以50-99％的产率提供了相应的α-氰基二羰基化合物，具有良好的对映选择性（87-97％ee）。
• Guanidinium iodide/urea hydrogen peroxide-catalyzed azidation of β-dicarbonyl compounds with trimethylsilyl azide
  作者：Koji Yasui、Kohei Kojima、Takanari Kato、Minami Odagi、Masaru Kato、Kazuo Nagasawa

  DOI：10.1016/j.tet.2016.07.015

  日期：2016.9

  We present an efficient synthesis of α-azido-β-dicarbonyl compounds from β-dicarbonyl compounds and trimethylsilyl azide, catalyzed by guanidinium hypoiodite. The reaction can be run in air at ambient temperature (up to 40 °C) and is not sensitive to moisture. The substrate scope is broad, including cyclic and linear β-dicarbonyl compounds, and the α-azide products are obtained in 55%–99% yield.

  我们提出了一种高效的合成方法，该方法由胍基次碘酸盐催化，由β-二羰基化合物和叠氮化三甲基硅烷基化物合成α-叠氮基-β-二羰基化合物。该反应可以在环境温度（最高40°C）的空气中进行，并且对水分不敏感。底物的适用范围很广，包括环状和线性的β-二羰基化合物，α-叠氮化物的产率为55％–99％。
• Ring-Strain-Enabled Catalytic Asymmetric Umpolung C–O Bond-Forming Reactions of 1,2-Oxazetidines for the Synthesis of Functionalized Chiral Ethers
  作者：Binyu Wu、Jinggang Yang、Min Gao、Lin Hu

  DOI：10.1021/acs.orglett.0c01916

  日期：2020.7.17

  An unprecedented catalytic asymmetric umpolung C–O bond-forming reaction of N-nosyl 1,2-oxazetidines with β-keto esters has been achieved in the presence of a chiral phase-transfer catalyst, allowing access to a range of highly functionalized chiral ethers bearing quaternary and no adjacent stereogenic centers with high yields, excellent enantioselectivities, and diastereoselectivities (up to 97% ee

  在手性相转移催化剂的存在下，N-烷基1,2-氧氮杂环丁烷与β-酮酯的空前催化不对称C-O键形成催化反应已经实现，从而可以使用一系列高度官能化的手性醚具有四元且没有相邻的立体发生中心，具有高产率，出色的对映选择性和非对映选择性（高达97％ee和20：1 dr）。这些多功能产品可以通过两个步骤灵活地转变为生物学上重要的手性融合和螺吗啉。
• Zirconium‐Salan Catalyzed Enantioselective <i>α</i> ‐Hydroxylation of <i>β</i> ‐Keto Esters
  作者：Jie Chen、Haiyang Gu、Xueying Zhu、Wonwoo Nam、Bin Wang

  DOI：10.1002/adsc.202000290

  日期：2020.7.29

  C2‐symmetric salan ligands and cumene hydroperoxide as an oxidant, affording synthetically valuable hydroxylation products in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee) under mild reaction conditions. In mechanistic studies, we have shown that (1) a Zr(IV)‐salan complex was generated in situ as the active catalyst responsible for the chiral induction, (2) the transfer

  我们在这里报告通过带有容易获得的C 2的Zr（IV）配合物对1-茚满酮衍生的β-酮酯的对映选择性和可扩展性α-羟基化的发展。对称的Salan配体和枯烯氢过氧化物作为氧化剂，在温和的反应条件下，可提供高收率（高达99％）和优异的对映选择性（高达99％ee）的合成有价值的羟基化产物。在机理研究中，我们表明（1）原位生成Zr（IV）-salan络合物作为负责手性诱导的活性催化剂，（2）亲电片段从氢过氧化枯烯向Zr（IV）的转移）结合的烯醇化物伴随有杂化的O-O键断裂，（3）salan配体的胺氢原子与氢过氧化枯烯的羟基之间形成氢键对于稳定立体控制的跃迁非常重要并提高对映选择性。

表征谱图