N-(tert-butoxycarbonyl)-N-(2-methyl-2-propenyl)-2-iodoaniline | 1407968-58-4

• 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: N-(tert-butoxycarbonyl)-N-(2-methyl-2-propenyl)-2-iodoaniline
• 英文别名: tert-butyl N-(2-iodophenyl)-N-(2-methylprop-2-enyl)carbamate
• CAS: 1407968-58-4
• 化学式: C₁₅H₂₀INO₂
• 分子量: 373.234
• InChiKey: KDIIXPMGBBNVHR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(tert-butoxycarbonyl)-N-(2-methyl-2-propenyl)-2-iodoaniline 在 tris-(dibenzylideneacetone)dipalladium(0) 、 1,1'-bis(di-tertbutylphosphino)ferrocene 、 草酰氯 、 caesium carbonate 、 三乙胺 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 40.33h， 生成 1-(tert-butoxycarbonyl)-3-methyl-2,3-dihydro-1H-quinolin-4-one
  参考文献：
  名称：

  Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study

  摘要：

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.

  DOI：

  10.1021/jo301924e
• 作为产物：
  描述：

  3-溴-2-甲基丙烯 、 N-Boc-2-碘苯胺 在 sodium hydride 作用下， 以 四氢呋喃 、 水 、 mineral oil 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 以69%的产率得到N-(tert-butoxycarbonyl)-N-(2-methyl-2-propenyl)-2-iodoaniline
  参考文献：
  名称：

  Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study

  摘要：

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.

  DOI：

  10.1021/jo301924e

文献信息

• Enantioselective CO ₂ Fixation Via a Heck‐Coupling/Carboxylation Cascade Catalyzed by Nickel
  作者：Alessandro Cerveri、Riccardo Giovanelli、Davide Sella、Riccardo Pedrazzani、Magda Monari、Olalla Nieto Faza、Carlos Silva López、Marco Bandini

  DOI：10.1002/chem.202101082

  日期：2021.5.17

  A novel asymmetric nickel‐based procedure has been developed in which CO2 fixation is achieved as a second step of a truncated Heck coupling. For this, a new chiral ligand has been prepared and shown to achieve enantiomeric excesses up to 99 %. The overall process efficiently furnishes chiral 2,3‐dihydrobenzofuran‐3‐ylacetic acids, an important class of bioactive products, from easy to prepare starting

  已经开发出一种新颖的基于镍的不对称程序，其中将CO 2固定作为截短的Heck偶联的第二步。为此，已经制备了新的手性配体，并显示出达到99％的对映体过量。整个过程从易于制备的起始原料有效地提供了重要的一类生物活性产品手性2,3-二氢苯并呋喃-3-基乙酸。实验和计算的共同努力揭示了催化循环的关键步骤，并暗示了Ni（I）物种意外参与偶联事件。
• Highly Enantioselective Cross-Electrophile Aryl-Alkenylation of Unactivated Alkenes
  作者：Zhi-Xiong Tian、Jin-Bao Qiao、Guang-Li Xu、Xiaobo Pang、Liangliang Qi、Wei-Yuan Ma、Zhen-Zhen Zhao、Jicheng Duan、Yun-Fei Du、Peifeng Su、Xue-Yuan Liu、Xing-Zhong Shu

  DOI：10.1021/jacs.9b03863

  日期：2019.5.8

  respect to data, studies have mainly focused on stereoconvergent reactions of racemic alkyl electrophiles. Here, we report an enantioselective cross-electrophile aryl-alkenylation reaction of unactivated alkenes. This method provides access to a number of biologically important chiral molecules such as dihydrobenzofurans, indolines, and indanes. The incorporated alkenyl group is suitable for further

  对映选择性交叉亲电试剂反应仍然是金属催化中的一个具有挑战性的课题，在数据方面，研究主要集中在外消旋烷基亲电试剂的立体会聚反应上。在这里，我们报告了未活化烯烃的对映选择性交叉亲电子芳基-烯基化反应。该方法提供了获得许多生物学上重要的手性分子的途径，例如二氢苯并呋喃、二氢吲哚和茚满。引入的烯基适用于可导致分子多样性和复杂性增加的进一步反应。该反应在室温下温和条件下进行，并且易于获得的手性辉石配体用于提供具有高对映选择性的产物。