Data for: "Transforming LiTMP lithiation of challenging diazines via gallium alkyl trans-metal-trapping"

The data set contains four files. These data relate to the research reported in the manuscript, “Transforming LiTMP lithiation of challenging diazines via gallium alkyl trans-metal-trapping” which has been published in Angewandte Chemie. The work was carried out in relation to the EPSRC grant, “Towards a paradigm shift in the principles and practice of polar organometallic chemistry” (EP/N011384/1), PI: Professor Eva Hevia; CI: Professor Robert E. Mulvey; and the European Research Council award (ERC-StG, MixMetApps) PI: Professor Eva Hevia; RA: Marina Uzelac. This chemistry can have important development implications in the field of aromatic and heteroaromatic functionalization. The investigation pioneers a new trans-metal-trapping (TMT) protocol based on a mixture of LiTMP (the base) and tris(trimethylsilylmethyl)gallium [Ga(CH2SiMe3)3, GaR3] (the trap) that, operating in a stepwise manner, is effective for the regioselective deprotonation of sensitive diazines in hydrocarbon solution as illustrated through reactions of three synthetically important diazines, namely pyrazine, pyridazine and pyrimidine, as well as through the well-known nitrogen-sulfur heterocycle benzothiazole. Providing valuable structural insight, all the metallo-activated complexes of these nitrogen heterocycles have been isolated and crystallographically characterized. Preliminary electrophilic quenching reactions have also been carried out. Files: 1. General Procedures. 2. NMR data 9a zip file containing data for 8 compounds. 3. CIF check (for X-ray crystallographic data). 4. MU_diazine_all.cif (for X-ray crystallographic data). Note that the NMR data file (2) containing raw data requires a specialist program such as Topspin or Mestrelab for opening; and the raw X-ray crystallographic data in file (4) requires a program such as Mercury, ORTEP-3, etc.

本数据集包含四个文件，相关数据对应发表于《Angewandte Chemie》的论文《通过烷基镓转金属捕获技术实现挑战性二嗪的LiTMP锂化反应》（Transforming LiTMP lithiation of challenging diazines via gallium alkyl trans-metal-trapping）中的研究工作。本研究依托英国工程与自然科学研究委员会（EPSRC）项目“迈向极性有机金属化学原理与实践的范式变革”（编号EP/N011384/1）开展，首席研究员（PI）为Eva Hevia教授，联合首席研究员（CI）为Robert E. Mulvey教授；同时得到欧洲研究委员会（ERC）初创型研究项目MixMetApps的资助，项目负责人为Eva Hevia教授，研究助理（RA）为Marina Uzelac。该研究方向在芳香族与杂芳香族官能化领域具有重要的开发应用价值。本工作首创了一种基于LiTMP（碱试剂）与三（三甲基硅基甲基）镓[Ga(CH2SiMe3)3，简称GaR3，捕获试剂]的新型转金属捕获（trans-metal-trapping, TMT）策略，该策略以分步模式实现烃类溶剂中敏感二嗪的区域选择性去质子化，通过吡嗪、哒嗪、嘧啶这三种合成上具有重要价值的二嗪以及经典氮硫杂环苯并噻唑的反应验证了该方法的有效性。本研究分离得到了所有氮杂环的金属活化配合物，并通过晶体学表征获取了宝贵的结构信息，同时还开展了初步的亲电淬灭反应实验。数据集包含的四个文件分别为：1. 通用实验步骤；2. NMR数据压缩包（内含8种化合物的相关数据）；3. X射线晶体学数据校验文件（CIF check）；4. MU_diazine_all.cif（X射线晶体学原始数据文件）。请注意，包含原始数据的NMR数据文件（文件2）需使用Topspin、Mestrelab等专业软件打开；文件4中的X射线晶体学原始数据则需借助Mercury、ORTEP-3等程序查看。