Polyketide natural products are an important class of biologically active compounds. Although substantial progress has been made on the synthesis of repetitive polyketide motifs through the iterative application of a single reaction type, synthetic access to more diverse motifs that require more than one type of carbon–carbon bond connection remains a challenge. Here we describe a catalytic, multicomponent method for the synthesis of the privileged polyketide 1,3-dienyl-6-oxy motif. The method allows for the formation of two new carbon–carbon bonds and two stereodefined olefins. It generates products that contain up to three contiguous sp³ stereocentres with a high stereoselectivity in a single operation and can be used to generate chiral products. The successful development of this methodology relies on the remarkable efficiency of the ruthenium-catalysed alkene–alkyne coupling reaction between readily available vinyl boronic acids and alkynes to provide unsymmetrical 3-boryl-1,4-diene reagents. In the presence of carbonyl compounds, these reagents undergo highly diastereoselective allylations to afford the desired 1,3-dienyl-6-oxy motif and enable complex polyketide synthesis in a rapid and asymmetric fashion.

聚酮化合物天然产物是一类重要的生物活性化合物。尽管通过重复应用单一反应类型在重复性聚酮化合物基序的合成方面已取得实质性进展，但合成获得需要多种碳-碳键连接的多种基序仍然是一个挑战。在这里，我们描述了一种催化的多组分方法，用于合成优先的聚酮1，3-二烯基-6-氧基基序。该方法可以形成两个新的碳-碳键和两个立体定义的烯烃。它生成的产品最多包含三个连续的sp ³在一次操作中具有高立体选择性的立体中心，可用于生成手性产物。该方法的成功开发依赖于现成的乙烯基硼酸和炔烃之间钌催化的烯烃-炔烃偶联反应的非凡效率，以提供不对称的3-硼基-1,4-二烯试剂。在羰基化合物存在下，这些试剂会经历高度非对映选择性的烯丙基化反应，以提供所需的1,3-二烯基-6-氧基基序，并能够以快速和不对称的方式合成复杂的聚酮化合物。