Yin Jianjun, Yuan Xiuping, Wang Simin, Shi Dazhen, Ma Shucheng, Zhu Lihan, Li Xiaoyu, Zhang Qian, Xiong Tao
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
J Am Chem Soc. 2025 Jul 23;147(29):25592-25602. doi: 10.1021/jacs.5c06354. Epub 2025 Jun 12.
Methods for the enantioselective transformations of alkenes constitute one of the most frequently used strategies in synthetic chemistry. Despite tremendous advancements in this domain, achieving the asymmetric difunctionalization of (/)-mixed alkenes in a stereoconvergent manner poses a formidable challenge. Here, we present a bimetallic relay-catalyzed asymmetric aminoboration of (/)-isomer mixtures with an engineered ferrocene-oxazoline (FcPHOX) ligand. The reactions proceed efficiently and exhibit a broad substrate scope with excellent enantio- and diastereoselectivity (generally >90% e.e. and up to 99:1 d.r.), affording chiral β-aminoalkylboronates as the key synthons for important bioactive molecules. The synthetic potential of this method is highlighted by the late-stage modification of complex molecules, versatile utility of these products, stereodivergent synthesis of four stereomers, and a sequence stereoconvergent aminoboration direct from propylbenzene. Experimental studies and density functional theory (DFT) calculations were conducted to elucidate the roles of two metal catalysts and crucial effect of the engineered ligand in origins of excellent enantio- and diastereoselectivities.
烯烃的对映选择性转化方法是合成化学中最常用的策略之一。尽管该领域取得了巨大进展，但以立体汇聚方式实现（±）-混合烯烃的不对称双官能化仍面临巨大挑战。在此，我们报道了一种双金属接力催化的（±）-异构体混合物与工程化二茂铁-恶唑啉（FcPHOX）配体的不对称氨基硼化反应。该反应高效进行，底物范围广泛，对映选择性和非对映选择性优异（通常对映体过量>90%，非对映体比例高达99:1），提供了作为重要生物活性分子关键合成子的手性β-氨基烷基硼酸酯。该方法的合成潜力体现在复杂分子的后期修饰、这些产物的多功能用途、四种立体异构体的立体发散合成以及直接从丙基苯进行的序列立体汇聚氨基硼化反应中。通过实验研究和密度泛函理论（DFT）计算，阐明了两种金属催化剂的作用以及工程化配体在优异对映选择性和非对映选择性起源中的关键作用。
