Jo Woohyun, Scholz Juliane K, Lyu Hairong, Cho Seung Hwan, Dong Guangbin
Department of Chemistry, University of Chicago, Chicago, IL, 60637, USA.
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 37673, Republic of Korea.
Angew Chem Int Ed Engl. 2025 May;64(21):e202503269. doi: 10.1002/anie.202503269. Epub 2025 Mar 27.
Despite the recent advancement, Matteson-type reactions are almost exclusively used to construct linear molecules. Herein we report an iterative boron-homologation approach to construct various carbocycles from a single precursor. This method utilizes an electron-withdrawing group (EWG) as a handle to enable intramolecular Matteson-type couplings, leading to diastereoselective and enantioselective ring formation. An intriguing role of the Lewis acid additive is identified. This approach proves to be general for preparing carbocycles with different ring sizes and multiple stereocenters. The annulation processes are also scalable, and the products can undergo various transformations to provide synthetically valuable structural motifs. In addition, this method can be extended to the preparation of diverse hard-to-make spirocyclic compounds from simple cyclic ketones. Moreover, an iterative approach to synthesize double spirocycles is also demonstrated.
尽管最近有了进展，但马特森型反应几乎仅用于构建线性分子。在此，我们报告了一种迭代硼同系化方法，可从单一前体构建各种碳环。该方法利用吸电子基团（EWG）作为手柄，实现分子内马特森型偶联，从而实现非对映选择性和对映选择性成环。确定了路易斯酸添加剂的一个有趣作用。该方法被证明对于制备具有不同环大小和多个立体中心的碳环具有通用性。环化过程也可扩展，并且产物可进行各种转化以提供具有合成价值的结构基序。此外，该方法可扩展到从简单环酮制备各种难以制备的螺环化合物。此外，还展示了一种合成双螺环的迭代方法。
