College of Science, Huazhong Agricultural University, Shizishan Avenue, Wuhan, 430070, P. R. China.
State Key Laboratory of Organometallic Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
Chemistry. 2023 Jan 12;29(3):e202202820. doi: 10.1002/chem.202202820. Epub 2022 Nov 24.
A three-component reaction of N, N-disubstituted aniline, α-diazo ester, and an allylic electrophile has been realized by [Rh(II)] /Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified α, α-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp )-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.
通过[Rh(II)]/Xantphos 催化，实现了 N，N-二取代苯胺、α-重氮酯和烯丙基亲电试剂的三组分反应，为各种含有二芳基烯丙基季铵中心的苯胺衍生物提供了直接的合成途径，产率良好。该反应的实用性通过产物的轻松衍生化来制备生物相关分子和结构支架得到了证明，这为增加分子多样性提供了很大的潜力。机理研究确定α，α-二芳基乙酸盐为活性中间体，从而揭示了在这种有吸引力的催化转化中存在苯胺衍生物/烯丙基烷基化级联的 C(sp3)-H 官能化。
