tert-butyl 2-diazo-2-(4-nitrophenyl)acetate | 29898-07-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl 2-diazo-2-(4-nitrophenyl)acetate
• CAS: 29898-07-5
• 化学式: C₁₂H₁₃N₃O₄
• 分子量: 263.253
• InChiKey: BFDUYWWANXRTED-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  74.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-diazo-2-(4-nitrophenyl)acetate 在 sodium tetrahydroborate 、 (3aS)-3,3-bis(3,5-dimethylphenyl)-1-naphthalen-1-yl-3a,4,5,6-tetrahydropyrrolo[1,2-c][1,3,2]oxazaborole;trifluoromethanesulfonic acid 作用下， 以 甲醇 、 丙腈 为溶剂， 反应 23.0h， 生成 tert-butyl 2-bromo-2-(hydroxymethyl)-1-(4-nitrophenyl)cyclopropanecarboxylate
  参考文献：
  名称：

  Oxazaborolidinium Ion-Catalyzed Cyclopropanation of α-Substituted Acroleins: Enantioselective Synthesis of Cyclopropanes Bearing Two Chiral Quaternary Centers

  摘要：

  A catalytic synthetic route to highly functionalized chiral cyclopropane derivatives was developed by Michael-initiated cyclopropanation of alpha-substituted acroleins with aryl- and alkyl diazoacetates. In the presence of chiral (S)-oxazaborolidinium cation 1b as a catalyst, the reaction proceeded in high yield (up to 93%) with high to excellent diastereoselectivity (up to 98% de) and enantio-selectivity (up to 95% ee).

  DOI：

  10.1021/ja209270e
• 作为产物：
  描述：

  对硝基苯乙酸 在 哌啶 、 对甲苯磺酰叠氮 、 硫酸 作用下， 以 吡啶 、 乙醚 为溶剂， 生成 tert-butyl 2-diazo-2-(4-nitrophenyl)acetate
  参考文献：
  名称：

  Schank,K., Chemische Berichte, 1970, vol. 103, p. 3093 - 3103

  摘要：

  DOI：

文献信息

• Neighboring group participation in carbene chemistry. Effect of neighboring carboxylate group on carbene reactivities
  作者：Hideo Tomioka、Katsuyuki Hirai、Kazuo Tabayashi、Shigeru Murata、Yasuji Izawa、Satoshi Inagaki、Takehiko Okajima

  DOI：10.1021/ja00177a033

  日期：1990.10

  the relative reactivities (k OH /k add ) being 0.3-0.5. In marked contrast, the «carboxylate» carbene generated from the sodium salt of the diazoacetate under the same conditions produces mostly the OH insertion product at the expense of the cyclopropanes, k OH /k add being >100. The marked effect of the carboxylate group is nicely explained in terms of the participation by the neighboring carboxylate

  （烷氧基羰基）卡宾的反应性显示出显着变化，因为一个人用羧酸酯基团取代了酯基团。因此，（甲氧基羰基）-或羧基（4-硝基苯基）卡宾，通过相应的重氮化合物在 2-甲基-2-丁烯和甲醇的二元混合物中的光解产生，将环加成产物提供给丁烯，而 OH 将产物插入到甲醇，相对反应性（k OH /k add ）为0.3-0.5。与此形成鲜明对比的是，在相同条件下由重氮乙酸钠盐生成的“羧酸盐”卡宾主要产生 OH 插入产物，但会消耗环丙烷，k OH /k add 大于 100。羧酸根的显着效果很好地解释了相邻羧酸根的参与，
• Rhodium-catalyzed enantioselective cyclopropanation of electron-deficient alkenes
  作者：Hengbin Wang、David M. Guptill、Adrian Varela-Alvarez、Djamaladdin G. Musaev、Huw M. L. Davies

  DOI：10.1039/c3sc50425e

  日期：——

  The rhodium-catalyzed reaction of electron-deficient alkenes with substituted aryldiazoacetates and vinyldiazoacetates results in highly stereoselective cyclopropanations. With adamantylglycine derived catalyst Rh2(S-TCPTAD)4, high asymmetric induction (up to 98% ee) can be obtained with a range of substrates. Computational studies suggest that the reaction is facilitated by weak interaction between

  缺电子的烯烃与取代的芳基重氮乙酸酯和乙烯基重氮乙酸酯的铑催化反应导致高度立体选择性的环丙烷化。使用金刚烷基甘氨酸衍生的催化剂Rh2（S-TCPTAD）4，可以在多种底物中获得高不对称诱导（高达98％ee）。计算研究表明，类胡萝卜素与底物羰基之间的弱相互作用促进了该反应，但随后根据羰基的性质通过不同的途径进行。丙烯酸酯和丙烯酰胺导致形成环丙烷化产物，同时使用不饱和醛和酮导致形成环氧化物。
• Correction to “Oxazaborolidinium Ion-Catalyzed Cyclopropanation of α-Substituted Acroleins: Enantioselective Synthesis of Cyclopropanes Bearing Two Chiral Quaternary Centers”
  作者：Lizhu Gao、Geum-Sook Hwang、Do Hyun Ryu

  DOI：10.1021/jacs.1c03211

  日期：2021.4.21

  reversed. The revised results were confirmed by NOE experiments and comparison of the optical rotation data with reported values after transformation. The corrected Table 3 is presented below. This correction does not affect the conclusion of the paper. Determined by 1H NMR analysis of the crude reaction mixture. Isolated yield. The ee of the product was determined by chiral HPLC or GC. Yield of the trans

  第20709和20710页。在该论文的已发布版本中，2w和2x的反式：顺式比例相反。通过NOE实验以及将旋光度数据与转换后报告的值进行比较，证实了修改后的结果。校正后的表3如下所示。此更正不影响本文的结论。通过1 H NMR分析粗反应混合物确定。孤立的产量。产物的ee通过手性HPLC或GC测定。反式异构体的收率由1计算分离的异构体混合物的1 H NMR分析。以43％的产率和94％的ee获得顺式异构体。获得了作为主要产物的顺式异构体，并且通过对分离的异构体混合物的1 H NMR分析来计算顺式异构体的产率。在提供实验细节的支持信息文件中，2w和2x的绝对配置被错误地绘制为（1 R，2 R）（第S26–S28页）。此处提供了经过更正的文件，该文件描述了（1 S，2 R）配置。可从https://pubs.acs.org/doi/10.1021/jacs.1c03211免费获得支持信息。 实验程序
• Rhodium-Catalyzed Formal C═O Bond Insertion and Sequential Acyl 1,4-N-to-O Migratory Rearrangement
  作者：Qiongya Li、Chunlan He、Jiahui Su、Ying Shao、Shengbiao Tang、Jiangtao Sun

  DOI：10.1021/acs.joc.2c02328

  日期：2022.12.16

  reaction between N-acyl pyridazinones and diazoacetates, leading to pyridazine derivatives in good yield under mild reaction conditions. This whole sequence probably proceeds through a carbene insertion into a C═O bond and an unprecedented 1,4-N-to-O acyl rearrangement reaction.

  我们在这里展示了N -酰基哒嗪酮和重氮乙酸盐之间的铑催化反应，在温和的反应条件下以良好的收率生成哒嗪衍生物。这整个序列可能通过卡宾插入 C=O 键和前所未有的 1,4 -N-to-O酰基重排反应进行。
• From C ₁ to C ₃ : Copper‐Catalyzed <i>gem</i> ‐Bis(trifluoromethyl)olefination of α‐Diazo Esters with TMSCF ₃
  作者：Qian Wang、Chuanfa Ni、Mingyou Hu、Qiqiang Xie、Qinghe Liu、Shitao Pan、Jinbo Hu

  DOI：10.1002/anie.202002409

  日期：2020.5.25

  AbstractA Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into “CuCF3” to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates.