McManus Caitilín, Crumpton Agamemnon E, Aldridge Simon
Inorganic Chemistry Laboratory, Dept of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Chem Commun (Camb). 2022 Jul 21;58(59):8274-8277. doi: 10.1039/d2cc02578g.
We report on the insertion of alkynes into heterometallic M-M' bonds, producing (aluminylalkenyl)copper compounds which possess differential reactivity at the two derived M-C functions. Uniquely, this system is capable of controlling access to isolable or dimetallated alkenes, by employing either kinetic or thermodynamic control. Subsequent derivatization with CO is both stereoselective (to systems) and regioselective (to Cu-C bonds), leading to the formation of the first structurally characterized examples of copper acyl compounds - aided by the cooperative reactivity of the proximal aluminium centre.
我们报道了炔烃插入异金属M-M'键中，生成（铝基烯基）铜化合物，该化合物在两个衍生的M-C官能团处具有不同的反应性。独特的是，该体系能够通过动力学或热力学控制来控制对可分离的或双金属化烯烃的获取。随后用CO进行衍生化反应既具有立体选择性（生成特定体系）又具有区域选择性（针对Cu-C键），在近端铝中心的协同反应性的帮助下，导致形成了首个具有结构表征的铜酰基化合物实例。
