Axially chiral tetrasubstituted alkenes are of increasing value and interest in chemistry-related areas. However, their catalytic asymmetric synthesis remains elusive, due to the high steric repulsion and relatively low conformational stability. Herein, we disclose the straightforward construction of atropisomeric tetrasubstituted alkenes via an effective enantiocontrol of vinyl cations. This copper-catalyzed enantioselective C(sp2)–H functionalization of sterically hindered (hetero)arenes with vinyl cations enables the efficient and atom-economical preparation of axially chiral acyclic tetrasubstituted styrenes and pyrrolyl ethylenes with high atroposelectivities. Importantly, this reaction represents the first example for the assembly of axially chiral alkenes through vinyl cation approach. Computational mechanistic studies reveal the reaction mechanism, origin of regioselectivity, Z/E selectivity and enantioselectivity. The synthetic utility has been demonstrated by diverse product derivatizations, chiral organocatalyst synthesis, as well as further applications in asymmetric catalysis.

中文翻译：

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通过铜催化的 C（sp2）-H 对映选择性合成轴向手性四取代烯烃芳烃与乙烯基阳离子的功能化


轴向手性四取代烯烃在化学相关领域的价值和兴趣越来越大。然而，由于高空间排斥力和相对较低的构象稳定性，它们的催化不对称合成仍然难以捉摸。在此，我们揭示了通过乙烯基阳离子的有效对映体控制来构建偏斜异构体四取代烯烃的直接构建。这种铜催化的对映选择性 C（sp2）-H 对位受阻（异）芳烃与乙烯基阳离子的功能化能够高效且原子经济地制备具有高反应选择性的轴向手性无环四取代苯乙烯和吡咯酰乙烯。重要的是，该反应代表了通过乙烯基阳离子方法组装轴向手性烯烃的第一个例子。计算机理研究揭示了反应机理、区域选择性的来源、Z/E 选择性和对映选择性。多种产品衍生化、手性有机催化剂合成以及在不对称催化中的进一步应用已经证明了合成的效用。