thiophen-2-ylmethyl diazoacetate | 1438843-10-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: thiophen-2-ylmethyl diazoacetate
• CAS: 1438843-10-7
• 化学式: C₇H₆N₂O₂S
• 分子量: 182.203
• InChiKey: SSNHAEBBQWMHMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.09
• 重原子数：
  12.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  62.7
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  thiophen-2-ylmethyl diazoacetate 在 重水 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以90%的产率得到thiophen-2-ylmethyl α-D-diazoacetate
  参考文献：
  名称：

  Synthesis of Structure and Function Diverse α-D-Diazoacetates, α-D-Diazoacetamides, α-D-Diazoketones, and the Antibiotic α-D-Azaserine

  摘要：

  Using 0.1 mol% to 1 mol% potassium carbonate in an acetonitrile-deuterium oxide mixture acts as a 'privileged' reaction system, which at ambient temperature affords, via a one-pot-one-cycle procedure, alpha-D-diazoacetates, alpha-D-diazoacetamides, or alpha-D-diazoketones from the corresponding nondeuterated form. The protocol is inexpensive, employs readily available materials, does not require harsh reaction conditions, requires two hours for completion, and affords the desired products in good yields and with excellent levels of deuterium incorporation. Exemplifying our protocol the first isotope labelled synthesis of N-Boc-alpha-D-azaserine with >= 95% D-incorporation is reported.

  DOI：

  10.1055/s-0032-1318136
• 作为产物：
  描述：

  2-Thienylmethyl bromoacetate 在 N,N′-双(对甲苯磺酰)肼 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 以47 %的产率得到thiophen-2-ylmethyl diazoacetate
  参考文献：
  名称：

  3-杂芳基双环[1.1.1]戊烷-1-乙酸酯的光催化三组分合成

  摘要：

  在此，我们报告了一种可见光诱导的三组分反应，涉及 [1.1.1] 丙烷、重氮酸盐和各种杂环化合物，用于合成 3-杂芳基双环 [1.1.1] 戊烷-1-乙酸酯。在整个反应过程中，重氮酸盐类物质产生的自由基在加成反应中与 [1.1.1] 丙烷反应形成双环 [1.1.1] 戊烷 (BCP) 自由基，随后与杂环反应，导致形成 1,3-双取代的 BCP 乙酸酯。值得注意的是，该方法具有出色的官能团相容性、高原子经济性和温和的反应条件，从而有助于合成 1,3-二取代的 BCP 乙酸酯。

  DOI：

  10.1021/acs.orglett.3c01213

文献信息

• Silver-Catalyzed Cross-Olefination of Donor and Acceptor Diazo Compounds: Use of<i>N</i>-Nosylhydrazones as Diazo Surrogate
  作者：Zhaohong Liu、Binbin Liu、Xue-Feng Zhao、Yan-Bo Wu、Xihe Bi

  DOI：10.1002/ejoc.201601610

  日期：2017.1.26

  The cross-olefination reaction of donor and acceptor diazo compounds is reported. The use of N-nosylhydrazones as the diazo surrogates and the dependence on silver catalysis are crucial for the reaction development. A variety of (hetero)aryl N-nosylhydrazones and α-diazo esters, amides, and phosphonates were compatible, affording functionalized alkenes in good-to-high yields with moderate Z/E selectivity

  报道了供体和受体重氮化合物的交叉烯烃化反应。使用 N-nosylhydrazones 作为重氮替代物和对银催化的依赖对于反应发展至关重要。各种（杂）芳基 N-nosylhydrazones 和 α-重氮酯、酰胺和膦酸酯是相容的，以良好到高的产率提供功能化烯烃，Z/E 选择性适中。实验和 DFT 计算结果表明交叉选择性是由于银催化剂对供体重氮化合物的选择性活化。
• A Three‐Component Reaction to Construct β‐Aminonitroso‐α‐Diazocarbonyl Compounds under Metal‐Free Conditions
  作者：Rongxiang Chen、Jihong Lan、Feng Li、Kai‐Kai Wang、Yinghui Xue、Canran Xu、Lantao Liu

  DOI：10.1002/adsc.202200025

  日期：2022.4.12

  A procedure for the transition-metal-free three-component reaction of 1,3,5-triazines, diazo compounds and tert-butyl nitrite has been described. This reaction goes through tandem nucleophilic attack to generate synthetically important β-aminonitroso-α-diazocarbonyl compounds in moderate to good yields. This protocol is distinguished by the use of readily available starting materials, wide substrate

  已经描述了 1,3,5-三嗪、重氮化合物和亚硝酸叔丁酯的无过渡金属三组分反应的程序。该反应通过串联亲核攻击以中等至高产率生成合成重要的 β-氨基亚硝基-α-重氮羰基化合物。该协议的特点是使用现成的起始材料、广泛的底物范围和操作简单。值得注意的是，NN键和CC键同时形成。
• Radical-carbene coupling reaction: Mn-catalyzed synthesis of indoles from aromatic amines and diazo compounds
  作者：Huihuang Li、Yanwei Zhao、Liang Ma、Meihua Ma、Jun Jiang、Xiaobing Wan

  DOI：10.1039/c7cc02440a

  日期：——

  An unprecedented coupling reaction between aromatic amines and diazo compounds was well developed, which afforded a bridge connecting between radical chemistry and metal carbene chemistry. This Mn-catalyzed tandem reaction also provided a fundamentally different and practical approach to the indole skeleton under mild conditions.

  芳香胺与重氮化合物之间空前的偶联反应已得到很好的发展，这为自由基化学和金属卡宾化学之间的桥梁提供了桥梁。这种锰催化的串联反应在温和条件下也为吲哚骨架提供了根本不同的实用方法。
• TBAI-Catalyzed S–H and N–H Insertion Reactions of α-Diazoesters with Thiophenols and Amines under Metal-Free Conditions
  作者：Rongxiang Chen、Guoyang Ma、Yawen Li、Jinju Zhang、Ran Xia、Kai-Kai Wang、Lantao Liu

  DOI：10.1021/acs.joc.2c01262

  日期：2022.8.19

  Mild, convenient, and effective TBAI-catalyzed S–H and N–H insertion reactions of α-diazoesters with thiophenols and aromatic amines under metal-free conditions have been described, furnishing a straightforward and general platform for the synthesis of various thioethers and 2-amino-2-oxoacetates in moderate to excellent yields. Moreover, this strategy features simple operation, mild conditions, broad

  已经描述了在无金属条件下温和、方便和有效的 TBAI 催化的 α-重氮酯与苯硫酚和芳香胺的 S-H 和 N-H 插入反应，为合成各种硫醚和 2 -amino-2-oxoacetates，产率适中至极好。此外，该策略具有操作简单、条件温和、底物范围广、易于放大等特点。
• Visible light-induced synthesis of 1,3-disubstituted bicyclo[1.1.1]pentane ketones<i>via</i>cooperative photoredox and N-heterocyclic carbene catalysis
  作者：Yan Gao、Zicong Zheng、Yu Zhu、Wenhao Xu、Yu Zhou、Chuanming Yu、Xinpeng Jiang

  DOI：10.1039/d3gc00643c

  日期：——

  While 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) represent an important class of bioisosteres with para-substituted aromatic rings, synthetic methods to access 1,3-disubstituted BCP ketones are still scarce throughout the literature. Herein, we report a cooperative N-heterocyclic carbene (NHC) and iridium dual-catalyzed three-component reaction involving radicals derived from diazo esters to perform

  虽然 1,3-二取代双环[1.1.1] 戊烷 (BCP) 代表了一类重要的具有对位取代芳环的生物等排体，但在整个文献中仍然缺乏获得 1,3-二取代 BCP 酮的合成方法。在此，我们报道了一种合作的 N-杂环卡宾 (NHC) 和铱双催化三组分反应，涉及衍生自重氮酯的自由基在 [1.1.1] 丙烷上进行加成反应以提供 BCP 自由基。然后与相应的 Breslow 中间基交叉偶联形成二取代的 BCP 酮。温和的条件、操作简单和高原子经济性使该方法成为一种强大的策略，可以从易于获得的起始材料中构建 1,3-二取代-BCP 酮，并具有合适的官能团耐受性。