Department of Chemistry, University of Basel, Johanns-Ring 19, 4056, Basel, Switzerland.
NCCR Molecular Systems Engineering, BPR 1095, Mattenstrasse 24a, 4058, Basel, Switzerland.
Angew Chem Int Ed Engl. 2022 Dec 19;61(51):e202211168. doi: 10.1002/anie.202211168. Epub 2022 Nov 17.
Alkene metathesis catalyzed by enantiopure metal alkylidene complexes enables exceptionally versatile strategies to products with configurationally-defined stereocenters. Desymmetrization processes thereby provide reliable stereoselective routes to aliphatic structures, while the differentiation of aromatic stereogenic units remained an outstanding challenge. Herein, we describe the feasibility of alkene metathesis to catalytically control stereogenic axes by traceless arene formation. Stereodynamic trienes are selectively converted into corresponding binaphthalene atropisomers upon exposure to a chiral molybdenum catalyst. Remarkably, stereoselective arene-forming metathesis allows enantioselectivities of up to 98 : 2 e.r. and excellent yields. As the disconnection of each bond of an aromatic target is retrosynthetically conceivable, it is anticipated that forging arenes by means of stereoselective metathesis will enable versatile approaches for the synthesis of a broad range of molecular topologies with precisely defined configuration.
手性金属亚烷基配合物催化的烯烃复分解反应为具有构型定义的立体中心的产物提供了非常通用的策略。因此，去对称化过程为脂肪族结构提供了可靠的立体选择性途径，而芳香族立体中心的区分仍然是一个突出的挑战。在这里，我们描述了通过无痕迹芳烃形成来催化控制立体轴的烯烃复分解反应的可行性。立体动态三烯在暴露于手性钼催化剂时选择性地转化为相应的联萘对映异构体。值得注意的是，立体选择性的芳族形成复分解允许高达 98 : 2 e.r. 和优异的产率。由于芳香族目标物的每个键的断开在回溯合成上都是可以想象的，因此，通过立体选择性复分解形成芳族化合物预计将为广泛的分子拓扑结构的合成提供通用的方法，这些结构具有精确定义的构型。
