Moreno-Rodriguez Nazaret, Borrego L Gabriel, Recio Rocío, Valdivia Victoria, Nicasio M Carmen, Álvarez Eleuterio, Khiar Noureddine, Fernández Inmaculada
Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Sevilla, C/Profesor García González, 2, 41012 Sevilla, Spain.
Departamento de Química Inorgánica, Universidad de Sevilla, Aptdo 1203, Sevilla, 41071, Spain.
Org Biomol Chem. 2023 Jul 19;21(28):5827-5839. doi: 10.1039/d3ob00816a.
A series of enantiopure chiral NH/SO palladium complexes have been synthesised with high yields by treating the corresponding -butylsulfinamide/sulfoxide derivatives with Pd(CHCN)Cl. The enantiopure chiral ligands were prepared by stereoselective addition of -butyl or phenyl methylsulfinyl carbanions to different -butylsulfinylimines. In all cases, coordination occurs with concomitant desulfinylation. X-ray studies of the Pd complexes showed a higher influence of the phenylsulfinyl group in comparison to that of the -butylsulfinyl group. Furthermore, we have obtained and characterised two possible palladium amine/sulfonyl complexes, epimers at sulfur, resulting from -desulfinylation and coordination of palladium with both oxygens of the prochiral sulfonyl group. The catalytic activity and enantioselectivity of the new Pd(II) complexes of acetylated amine/-butyl- and phenylsulfoxides in the carboxylated cyclopropanes arylation reaction has been studied, obtaining the best results with the phenylsulfoxide ligand 25(SC,SS) that produced the final arylated product in a 93 :7 enantiomeric ratio.
通过用Pd(CHCN)Cl处理相应的丁基亚磺酰胺/亚砜衍生物，以高收率合成了一系列对映体纯的手性NH/SO钯配合物。对映体纯的手性配体是通过将丁基或苯基甲基亚磺酰基碳负离子立体选择性地加成到不同的丁基亚磺酰基亚胺上制备的。在所有情况下，配位伴随着脱硫酰基化反应发生。钯配合物的X射线研究表明，与丁基亚磺酰基相比，苯基亚磺酰基的影响更大。此外，我们已经获得并表征了两种可能的钯胺/磺酰基配合物，它们是硫上的差向异构体，由脱硫酰基化反应以及钯与前手性磺酰基的两个氧原子配位而产生。研究了乙酰化胺/丁基和苯基亚砜的新型钯(II)配合物在羧基化环丙烷芳基化反应中的催化活性和对映选择性，使用苯基亚砜配体25(SC,SS)获得了最佳结果，该配体以93:7的对映体比例生成了最终的芳基化产物。
