Markovnikov Protoborylation of Unactivated Terminal Alkenes via Copper-Guanidine Catalysis

作者：Jin Tao, Yicen Ge, Ai Zhang, Ge Lin, Huangfeng Zhang, Siyu Jiang, Jianmin Chen, Xiaoyan Ma, Jinghua Tang, Jin‐Yu Liu · 发表于：The Journal of Organic Chemistry · 年份：2025 · DOI：10.1021/acs.joc.5c00691 · 被引用次数：3 · 研究领域：Organoboron and organosilicon chemistry、Chemical Synthesis and Analysis、Catalytic Cross-Coupling Reactions

Herein copper-catalyzed Markovnikov protoborylation of unactivated terminal alkenes was achieved through the employment of a bulky σ-donating guanidine ligand. The reaction demonstrated good tolerance to diverse functional groups and remarkable selectivity for branched borylation products (86:14-97:3) under ambient conditions, which enabled the synthesis of secondary alkyl boronates in grams with further valuable derivatizations. Mechanistic studies suggested the boryl insertion to C═C bonds via Cu-guanidine complex and ruled out the possibility of a diboration-protodeboronation process.