Cuenca Ana B, Montserrat Sergi, Hossain Kabir M, Mancha Gisela, Lledós Agustí, Medio-Simón Mercedes, Ujaque Gregori, Asensio Gregorio
Departamento de Química Orgánica, Universidad de Valencia, 46100 Burjassot, Valencia, Spain.
Org Lett. 2009 Nov 5;11(21):4906-9. doi: 10.1021/ol9020578.
The reaction between acetylenes and sulfoxides, studied as a test case for gold-catalyzed intermolecular addition, provides the oxyarylation compounds 3 in good yields. Unpredictably, in all cases a single regioisomer arising from the electrophilic aromatic alkylation at the position adjacent to the sulfur atom is obtained instead of the expected Friedel-Crafts regioisomer. A new concerted mechanism based on DFT calculations is proposed to account for the products in this intermolecular gold(I)-catalyzed reaction.
作为金催化分子间加成的一个测试案例，对乙炔与亚砜之间的反应进行了研究，该反应以良好的产率得到了氧芳基化化合物3。出乎意料的是，在所有情况下，得到的都是在与硫原子相邻位置发生亲电芳香烷基化产生的单一区域异构体，而不是预期的傅-克区域异构体。基于密度泛函理论计算提出了一种新的协同机理，以解释该分子间金（I）催化反应中的产物。
