Zhang Kai-Xiang, Liu Mei-Yu, Yao Bo-Ying, Zhou Qi-Lin, Xiao Li-Jun
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
J Am Chem Soc. 2024 Aug 14;146(32):22157-22165. doi: 10.1021/jacs.4c07907. Epub 2024 Aug 5.
Stereoconvergent reactions enable the transformation of mixed stereoisomers into well-defined, chiral products─a crucial strategy for handling /-mixed olefins, which are common but challenging substrates in organic synthesis. Herein, we report a stereoconvergent and highly enantioselective method for synthesizing -homoallylic alcohols via the nickel-catalyzed reductive coupling of /-mixed 1,3-dienes with aldehydes. This process is enabled by an -heterocyclic carbene ligand characterized by -symmetric backbone chirality and bulky 2,6-diisopropyl -aryl substituents. Our method achieves excellent stereocontrol over both enantioselectivity and -selectivity in a single step, producing chiral -homoallylic alcohols that are valuable in natural products and pharmaceuticals.
立体汇聚反应能够将混合立体异构体转化为结构明确的手性产物，这是处理外消旋烯烃的关键策略，外消旋烯烃在有机合成中很常见但具有挑战性。在此，我们报道了一种通过镍催化的外消旋1,3-二烯与醛的还原偶联来合成β-高烯丙醇的立体汇聚且高度对映选择性的方法。该过程由一种具有α-对称主链手性和庞大的2,6-二异丙基-α-芳基取代基的α-杂环卡宾配体实现。我们的方法在一步反应中对映选择性和非对映选择性均实现了出色的立体控制，生成了在手性天然产物和药物中具有重要价值的手性β-高烯丙醇。
