Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, Tamil Nadu, India.
Org Lett. 2021 Apr 16;23(8):2964-2970. doi: 10.1021/acs.orglett.1c00646. Epub 2021 Apr 5.
An efficient Rh(III)-catalyzed aerobic oxidative C-H alkenylation of arylamides with unactivated alkenes is described. The olefination reaction was compatible with various substituted arylamides including primary, secondary, and tertiary as well as functionalized unactivated olefins. Meanwhile, ortho mono/bis-alkylated arylamides were synthesized in the reaction of arylamides with norbornene. In the alkenylation reaction, molecular oxygen along with organic acid was used to regenerate the active catalyst for the next catalytic cycle. A possible reaction mechanism involving C-H activation/insertion/β-hydride elimination followed by aerobic oxidation was proposed and supported by the deuterium labeling studies.
描述了一种高效的 Rh(III)-催化的芳酰胺与未活化烯烃的有氧氧化 C-H 烯丙基化反应。该烯烃化反应与各种取代的芳酰胺相容，包括伯、仲和叔芳酰胺以及功能化的未活化烯烃。同时，在芳酰胺与降冰片烯的反应中合成了邻位单/双烷基化的芳酰胺。在烯丙基化反应中，使用分子氧和有机酸来再生活性催化剂，用于下一个催化循环。提出了一种可能的反应机理，涉及 C-H 活化/插入/β-氢化物消除，然后是有氧氧化，并通过氘标记研究得到支持。
