CF₃-containing multi-borylated compounds are intriguing molecules that can serve as building blocks and readily transform into various significant molecules. Here, a series of Cu-catalyzed assembly of 1,3- and 1,4-diborylated compounds bearing CF₃ group starting from readily available 1,3-enynes has been developed. This is the first example that could approach two different C–B bonds from 1,3-enynes despite their conjugated structures. The unprecedented regio- and stereodivergent sp²/sp³ 1,3- and 1,4-diborylations of 1,3-enynes were regulated by ligands, bases, and solvents. Most remarkably, the well-known defluorination of CF₃ group on alkenes upon nucleophilic additions was completely suppressed in our systems, leaving a valuable CF₃ group intact. Moreover, homopropargylic boronates and homoallenyl boronates as the key intermediates for the above transformations were also obtained after fine-tuning the reaction conditions. Both experimental and theoretical calculations elucidate the E/Z selectivities and regioselectivities in these transformations.

含CF ₃的多硼化化合物是引人入胜的分子，可以充当构建基块并轻松转化为各种重要分子。在此，已经开发了一系列从易获得的1，3-烯炔开始的带有CF ₃基团的1，3-和1，4-二硼化的化合物的铜催化组装体。这是第一个示例，尽管它们具有共轭结构，但仍可从1，3-炔烃接近两个不同的C-B键。1,3-烯炔的史无前例的区域和立体发散的sp ² / sp ³ 1,3-和1,4-二硼烷基化受到配体，碱和溶剂的调节。最引人注目的是CF _3的脱氟在我们的系统中，亲核加成后烯烃上的碳原子团被完全抑制，留下了宝贵的CF ₃基团。此外，在微调反应条件之后，还获得了作为上述转化的关键中间体的均炔丙基硼酸酯和均烯丙基硼酸酯。实验和理论计算都阐明了这些转化中的E / Z选择性和区域选择性。