Denisenko Irina N, Varzatskii Oleg A, Selin Roman A, Belov Alexander S, Lebed Ekaterina G, Vologzhanina Anna V, Zubavichus Yan V, Voloshin Yan Z
Vernadskii Institute of General and Inorganic Chemistry NASU 03142 Kiev Ukraine.
PBMR Labs Ukraine 02094 Kiev Ukraine.
RSC Adv. 2018 Apr 11;8(24):13578-13587. doi: 10.1039/c8ra01819g. eCollection 2018 Apr 9.
A new approach for performing Suzuki-Miyaura and Sonogashira reactions of iron(ii) dihalogenoclathrochelates, optimizing their reaction conditions (such as temperature, solvent and a palladium-containing catalyst) and the nature of other reagents (such as arylboron components) is elaborated. These palladium-catalyzed reactions are very sensitive to the nature of the macrobicyclic substrates. The reactivity of the leaving halogen atoms correlates with their ability to undergo an oxidative addition, decreasing in the order: I > Br > Cl, and iron(ii) diiodoclathrochelate underwent these C-C cross-couplings under their "classical" conditions. Phenylboronic, 4-carboxyphenylboronic and 6-ethoxy-2-naphthylboronic acids, and the diethyl ether of 4-(ethoxycarbonyl)boronic acid were tested as components of Suzuki-Miyaura reactions in DMF and in THF. The highest yields of the target products were obtained in DMF, while the highest activation was observed with sodium and potassium carbonates. The Suzuki-Miyaura reaction of a diiodoclathrochelate with 6-ethoxy-2-naphthylboronic acid gave the mono- and difunctionalized clathrochelates resulting from the tandem hydrodeiodination - C-C cross-coupling and double C-C cross-coupling reactions, respectively. Its Sonogashira reactions with trimethylsilylacetylene and acetylenecarboxylic acid in THF and in DMF were tested. This palladium-catalyzed reaction with a (CH)Si-containing active component gave the target products in a high total yield. The complexes obtained were characterized using elemental analysis, MALDI-TOF, UV-Vis, H and C{H} NMR spectroscopy, and by single crystal XRD. Despite the non-equivalence of the ribbed α-dioximate fragments of their molecules, the encapsulated iron(ii) ion is situated almost in the centre of its FeN-coordination polyhedron, the geometry of which is almost intermediate between a trigonal prism and a trigonal antiprism.
阐述了一种用于进行铁（II）二卤代笼形螯合物的铃木-宫浦反应和索尼加希拉反应的新方法，优化了它们的反应条件（如温度、溶剂和含钯催化剂）以及其他试剂的性质（如芳基硼组分）。这些钯催化反应对大环底物的性质非常敏感。离去卤原子的反应活性与其进行氧化加成的能力相关，顺序为：I＞Br＞Cl，并且铁（II）二碘笼形螯合物在其“经典”条件下进行了这些碳-碳交叉偶联反应。测试了苯硼酸、4-羧基苯硼酸和6-乙氧基-2-萘硼酸以及4-（乙氧基羰基）硼酸二乙醚作为在N，N-二甲基甲酰胺（DMF）和四氢呋喃（THF）中铃木-宫浦反应的组分。在DMF中获得了目标产物的最高产率，而使用碳酸钠和碳酸钾时观察到最高的活化作用。二碘笼形螯合物与6-乙氧基-2-萘硼酸的铃木-宫浦反应分别通过串联加氢脱碘-碳-碳交叉偶联和双碳-碳交叉偶联反应得到了单官能化和双官能化的笼形螯合物。测试了其在THF和DMF中与三甲基硅乙炔和乙炔羧酸的索尼加希拉反应。这种与含（CH）Si活性组分的钯催化反应以高总产率得到了目标产物。使用元素分析、基质辅助激光解吸电离飞行时间质谱（MALDI-TOF）、紫外可见光谱、氢谱和碳-氢相关谱（C{H} NMR）以及单晶X射线衍射（XRD）对所得配合物进行了表征。尽管其分子的带肋α-二肟片段不相等，但包封的铁（II）离子几乎位于其FeN配位多面体的中心位置，其几何形状几乎介于三角棱柱和三角反棱柱之间。
