College of Chemistry and Environmental Science, Inner Mongolia Key Laboratory of Green Catalysis, Inner Mongolia Normal University, Hohhot, 010022, China.
Chem Commun (Camb). 2021 Oct 26;57(85):11229-11232. doi: 10.1039/d1cc04121e.
The regiodivergent catalytic dehydrogenative cross-coupling reactions at both sp and sp hybridized carbons of aromatic compounds are particularly challenging. Herein, we report the finding of transient directing group controlled regiodivergent C(sp)-C(sp) and C(sp)-C(sp) cross-coupling in the -methyl benzaldehyde frameworks. Catalyzed by palladium, using KSO or [F] reagents as by-standing oxidants and unactivated arenes as substrates/solvents, various benzyl benzaldehydes or phenyl benzaldehydes were prepared. A mechanism study indicated that the regiospecificity is dominated by the [5,6]-fused palladacycle or [6,5]-fused palladacycle intermediates, which are generated from Pd-chelation with specified transient directing groups and further C-H activations.
芳香族化合物中 sp 和 sp 杂化碳原子的区域发散催化脱氢交叉偶联反应特别具有挑战性。在此，我们报告了在 -甲基苯甲醛框架中瞬态导向基团控制的 C(sp)-C(sp)和 C(sp)-C(sp)交叉偶联的发现。在钯的催化作用下，使用 KSO 或 [F]试剂作为旁观氧化剂，未活化的芳烃作为底物/溶剂，制备了各种苄基苯甲醛或苯甲醛。机理研究表明，区域选择性由[5,6]-稠合钯环或[6,5]-稠合钯环中间体决定，它们是由特定瞬态导向基团与钯螯合并进一步 C-H 活化生成的。
