Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2020-09-28 , DOI: 10.1016/j.jorganchem.2020.121545 Yuki Murata , Naoki Kakusawa , Yukako Arakawa , Yukako Hayashi , Shun Morinaga , Masaaki Ueda , Tadashi Hyodo , Mio Matsumura , Kentaro Yamaguchi , Jyoji Kurita , Shuji Yasuike
The Pd-catalyzed cross-coupling reactions of Sb-aryl-1,5-azastibocines with alkenes are described. The reactions of azastibocines with alkenes such as vinyl ketones, alkenes, and acrylates in the presence of 10 mol% PdCl2 at 80 °C in DMA under aerobic conditions produced Heck adducts in moderate-to-excellent yields. Single-crystal X-ray and NMR analysis revealed that the aryl donors in this reaction, the Sb-aryl-1,5-azastibocines, are hypervalent compounds that display N–Sb intramolecular non-bonding interaction. These are the first examples of Pd-catalyzed Heck-type arylations using heterocyclic hypervalent organoantimony compounds. Although the reactions proceeded efficiently with the azastibocines, they hardly progressed with trivalent and pentavalent triarylantimony reagents.
中文翻译:
Pd催化的氧化乙烯基酮,烯烃,和与丙烯酸酯的的Heck型芳基化锑-芳基- tetrahydrodibenz [ C,F ] [1,5] azastibocines
的Pd催化交联偶合反应的Sb与烯烃-芳基-1,5- azastibocines中描述。氮杂stibocines与烯烃(如乙烯基酮,烯烃和丙烯酸酯)在10 mol%PdCl 2存在下,在DMA中于80°C在好氧条件下反应,可产生中等至优异的Heck加合物。单晶X射线和NMR分析表明,该反应中的芳基供体Sb-芳基-1,5-氮杂双胍酮是显示N–Sb分子内非键相互作用的高价化合物。这些是使用杂环高价有机锑化合物进行Pd催化的Heck型芳基化的第一个实例。尽管用氮杂stibocines可使反应有效地进行,但它们几乎不与三价和五价三芳基锑试剂一起进行。