The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. The stereoselective 1,4-functionalization of 1,3-enynes, a prevalent synthon in synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on the ionic reaction pathway. The radical-involved asymmetric 1,4-functionalization of 1,3-enynes remains a prominent challenge. Herein, we describe the asymmetric three-component 1,4-dialkylation of 1,3-enynes via dual photoredox and chromium catalysis to provide chiral allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, and simultaneous control of axial and central chiralities. Mechanistic studies suggest that this reaction proceeds through a radical-involved redox-neutral pathway.

在过去的十年中，光氧化还原和过渡金属催化的结合已发展成为有机合成的强大平台。1,3-烯炔（合成化学中普遍存在的合成子）的立体选择性1,4-官能化可以提供有价值的手性丙二烯衍生物。然而，巨大的努力已经集中在离子反应途径上。1,3-烯炔的自由基参与的不对称1,4-官能化仍然是一个突出的挑战。在此，我们描述了通过双光氧化还原和铬催化对 1,3-烯炔进行不对称三组分 1,4-二烷基化以提供手性烯醇。该方法具有原料易得、底物范围广、官能团相容性好、区域选择性高以及同时控制轴向和中心手性等特点。