Department of Fine Chemistry, Seoul National University of Science and Technology, 232 Gongneung-ro, Nowon-gu, Seoul 01811, Korea.
J Org Chem. 2022 May 20;87(10):6552-6561. doi: 10.1021/acs.joc.2c00116. Epub 2022 May 9.
Imines are important building blocks in organic chemistry. Iminines, aldimines and ketimines, have been traditionally synthesized by the condensation reaction of the corresponding carbonyl compound with an amine moiety. More recently, palladium-catalyzed synthesis of ketimines using imidoyl chlorides has been reported. As an alternative, we report the reversed-polarity synthesis of sulfonyl ketimines using an anion equivalent imidoylsilane as a new nucleophilic coupling partner in the presence of a palladium catalyst. To the best of our knowledge, this is the first report of the use of imidoylsilanes in transition-metal-catalyzed coupling reactions. Diaryliodonium salt as an electrophile, various aryl-aryl or heteroaryl-aryl -sulfonyl ketimines were successfully prepared in up to 99% isolated yields.
亚胺是有机化学中的重要结构单元。亚胺、醛亚胺和酮亚胺通常是通过相应的羰基化合物与胺部分的缩合反应来合成的。最近，已有报道使用亚酰氯钯催化合成酮亚胺。作为替代方法，我们报告了在钯催化剂存在下，使用阴离子等价物亚胺基硅烷作为新的亲核偶联试剂，以反极性方式合成砜基酮亚胺。据我们所知，这是首次报道在过渡金属催化偶联反应中使用亚胺基硅烷。二芳基碘鎓盐作为亲电试剂，各种芳基-芳基或杂芳基-芳基-砜基酮亚胺以高达 99%的分离收率成功制备。
