Benzofuran is a key structural motif due to its bioactivity and frequent occurrence in nature. Although C−H functionalization can be one of the most efficient methods to synthesize poly‐substituted benzofurans, C6‐selective C−H functionalization has been undeveloped so far. Herein we report aluminum‐mediated C6‐selective linear alkylation of 2‐carbamoylbenzofurans with 1‐alkenes by nickel/N‐heterocyclic carbene catalysis. In the presence of a bulky aluminum additive [(2,6‐tBu₂‐4‐Me‐C₆H₂O)₂AlMe] (MAD), N,N‐diisobutylbenzofuran‐2‐carboxamide undergoes the C6‐selective linear alkylation reaction. Different terminal alkenes can afford the corresponding C6‐alkylation products in moderate to high yields. The site‐selectivity can be understood in terms of both steric and electronic factors.

中文翻译：

---

镍催化铝介导的2-氨基甲酰基苯并呋喃的C6-选择性C-H烷基化

苯并呋喃由于其生物活性和在自然界中频繁发生而成为关键的结构基序。尽管C H官能化可以是合成多取代苯并呋喃的最有效方法之一，但迄今为止C6选择性C H官能化尚未开发。本文中，我们报道了镍/ N-杂环卡宾催化铝介导的2-氨基甲酰基苯并呋喃与1-烯烃的C6选择性线性烷基化反应。存在大量铝添加剂[（_2,6 - t Bu ₂ -4-Me-C ₆ H ₂ O）₂ AlMe]（MAD），N，N二异丁基苯并呋喃-2-羧酰胺经历C6选择线性烷基化反应。不同的末端烯烃可以以中等至高收率提供相应的C6-烷基化产物。可以通过空间因素和电子因素来理解位点选择性。