Two-component C–H bond additions to a large variety of coupling partners have been developed with applications towards materials, natural product and drug synthesis. Sequential three-component C–H bond addition across two different coupling partners potentially enables the convergent synthesis of complex molecular scaffolds from simple precursors. Here, we report three-component Co(iii)-catalysed C–H bond additions to dienes and aldehydes that proceed with high regio- and stereoselectivity, resulting in two new carbon–carbon σ-bonds and four to six new stereocentres. The reaction relies on the synergistic reactivity of the diene and aldehyde, with neither undergoing C–H bond addition alone. A detailed mechanism is supported by X-ray structural characterization of a Co(iii)-allyl intermediate, observed transfer of stereochemical information, and kinetic isotope studies. The applicability of the method to biologically relevant molecules is exemplified by the rapid synthesis of the western fragment of the complex ionophore antibiotic lasalocid A.

已经开发了向多种偶联伙伴中添加两组分的C–H键，并将其应用于材料，天然产物和药物合成。在两个不同的偶联配偶体之间连续的三组分C–H键加成潜在地实现了从简单前体的聚合分子支架的融合合成。在这里，我们报告了在二烯和醛中三组分Co（iii）催化的C–H键加成，并具有较高的区域选择性和立体选择性，从而产生了两个新的碳-碳σ键和四个至六个新的立体中心。该反应依赖于二烯和醛的协同反应性，两个都不单独进行C–H键加成。Co（iii）的X射线结构表征支持了详细的机理）-烯丙基中间体，观察到的立体化学信息传递，以及动力学同位素研究。该方法对生物学相关分子的适用性以复合离子载体抗生素拉索洛西德A的西方片段的快速合成为例。