Orthogonal Selectivity in C–H Olefination: Synthesis of Branched Vinylarene with Unactivated Aliphatic Substitution

Oxidative
coupling is a useful tool to synthesize vinylarenes.
Despite remarkable successes in linear vinylarene, branched vinylarene
synthesis has remained underdeveloped. Overcoming this limitation,
herein, we report a chelation-assisted oxidative coupling to generate
branched olefinated product in high yield. Exclusive branched selectivity
was obtained using alkenyl carboxylic acid. Detailed experimental
studies combined with computational investigations suggest that β-migratory
insertion, followed by a decarboxylation pathway is operative for
the overall transformation.

氧化偶联是合成乙烯基芳烃（vinylarenes）的重要手段。尽管在线性乙烯基芳烃的合成领域已取得显著进展，但支化乙烯基芳烃的合成仍未得到充分发展。为克服这一局限，本文报道了一种螯合辅助氧化偶联策略，可高收率得到支化烯烃化产物。以烯基羧酸为底物时，可获得专属支化选择性。详尽的实验研究结合计算模拟分析表明，该整体转化过程遵循β-迁移插入后脱羧的反应路径。