The controlled isomerization and functionalization of alkenes is a cornerstone achievement in organometallic catalysis that is now widely used throughout industry. In particular, the addition of CO and H₂ to an alkene, also known as the oxo-process, is used in the production of linear aldehydes from crude alkene feedstocks. In these catalytic reactions, isomerization is governed by thermodynamics, giving rise to functionalization at the most stable alkylmetal species. Despite the ubiquitous industrial applications of tandem alkene isomerization/functionalization reactions, selective functionalization at internal positions has remained largely unexplored. Here we report that the simple W(0) precatalyst W(CO)₆ catalyses the isomerization of alkenes to unactivated internal positions and subsequent hydrocarbonylation with CO. The six- to seven-coordinate geometry changes that are characteristic of the W(0)/W(II) redox cycle and the conformationally flexible directing group are key factors in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for in situ functionalization.

烯烃的受控异构化和功能化是有机金属催化领域的一项基石成就，现已广泛应用于整个工业领域。_{特别是，将 CO 和 H 2}添加到烯烃中，也称为羰基合成法，用于从粗烯烃原料生产直链醛。在这些催化反应中，异构化受热力学控制，导致最稳定的烷基金属物种发生官能化。尽管串联烯烃异构化/功能化反应的工业应用无处不在，但内部位置的选择性功能化在很大程度上仍未得到探索。在这里，我们报告了简单的 W(0) 预催化剂 W(CO) ₆催化烯烃异构化为未活化的内部位置并随后与 CO 发生烃基化。具有 W(0)/W(II) 氧化还原循环特征的六到七坐标几何变化和构象灵活的导向基团是关键因素允许异构化发生在多个位置，并停止在为原位功能化做好准备的定义的未激活内部位点。