Kyriakakis Georgios, Kidonakis Marios, Louka Anastasia, Stratakis Manolis
Department of Chemistry, University of Crete, Voutes, 71003 Heraklion, Greece.
J Org Chem. 2024 Feb 2;89(3):1980-1988. doi: 10.1021/acs.joc.3c01500. Epub 2024 Jan 12.
In the presence of catalytic amounts of Pd nanoparticles, generated from Pddba/Ag(I), -1,2-ditrimethylsilylarylethylenes undergo with aryl iodides a stereospecific Mizoroki-Heck arylation leading to -ditrimethylsilyldiarylethylenes. This chemoselectivity is in contrast to that of their trimethylgermyl analogues, which are arylated at the position of the C-Ge bonds. -1,2-Ditrimethylsilylarylethylenes are completely unreactive under the standard reaction conditions. The reaction tolerates the presence of boryl, silyl, or bromine substituents on the aryl iodides. From a mechanistic point of view, the process involves -arylpalladation followed by -dehydropalladation.
在由双(二亚苄基丙酮)钯/银(I)生成的催化量钯纳米颗粒存在下，-1,2-二(三甲基硅基)芳基乙烯与芳基碘发生立体选择性的宫泽-赫克芳基化反应，生成-二(三甲基硅基)二芳基乙烯。这种化学选择性与其三甲基锗类似物相反，后者在碳-锗键的位置发生芳基化反应。-1,2-二(三甲基硅基)芳基乙烯在标准反应条件下完全无反应活性。该反应可容忍芳基碘上存在硼基、硅基或溴取代基。从机理角度来看，该过程涉及-芳基钯化，随后是-脱氢钯化。
