Asymmetric ring-expansion reactions of silacyclobutanes (SCBs) with alkynes have evolved as one of the powerful protocols for the construction of silicon-stereogenic compounds. However, the achievement of highly enantioselective annulation of SCBs with terminal alkynes remains a challenge. Herein, we report a rhodium-catalyzed asymmetric annulation reaction of SCBs with terminal alkynes, which relies on the newly identified chiral sulfinamide phosphine ligand Ming-Phos. This catalytic system exhibits unique effects under mild conditions, leading to the direct synthesis of structurally diverse chiral silacycles in moderate to good yields with high enantioselectivities (up to 95% ee).

硅杂环丁烷（SCB）与炔烃的不对称扩环反应已发展成为构建硅立体化合物的强大方案之一。然而，实现SCB与末端炔烃的高度对映选择性环化仍然是一个挑战。在此，我们报道了铑催化的SCB与末端炔烃的不对称环化反应，该反应依赖于新鉴定的手性亚磺酰胺膦配体Ming-Phos。该催化体系在温和条件下表现出独特的效果，可以直接合成结构多样的手性硅环化合物，产率中等至良好，具有高对映选择性（高达 95% ee）。