Roh Byeongdo, Farah Abdikani Omar, Kim Beomsu, Feoktistova Taisiia, Moeller Finn, Kim Kyeong Do, Cheong Paul Ha-Yeon, Lee Hong Geun
Department of Chemistry, Seoul National University, Seoul 08826, Korea.
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331-2145, United States.
J Am Chem Soc. 2023 Apr 5;145(13):7075-7083. doi: 10.1021/jacs.3c00637. Epub 2023 Mar 2.
A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level of enantiospecificity to allow facile access to synthetically challenging and valuable chiral ketones and carboxylic acid derivatives. The use of a sterically encumbered and electron-rich phosphine ligand proved to be crucial for the success of the reaction. Furthermore, on the basis of experimental and computational studies, a unique mechanism for the transmetalation, assisted by the noncovalent interactions of the C(sp)-based organoboron reagent, has been identified.
已开发出一种用于对映体富集的烷基硼化合物进行立体选择性钯催化酰基交叉偶联的新策略。该方案具有极高的对映体选择性水平，能够轻松获得合成上具有挑战性且有价值的手性酮和羧酸衍生物。事实证明，使用空间位阻大且富电子的膦配体对于反应的成功至关重要。此外，基于实验和计算研究，已确定了一种独特的转金属化机制，该机制由基于C(sp)的有机硼试剂的非共价相互作用辅助。
