Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, Westlake University, Hangzhou, 310024, Zhejiang Province, China.
Institute of Natural Sciences, Westlake Institute for Advanced Study, Hangzhou, 310024, Zhejiang Province, China.
Nat Commun. 2022 Aug 26;13(1):5036. doi: 10.1038/s41467-022-32614-4.
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融合已经发展成为有机合成中的一个强大平台。1,3-烯炔作为合成化学中常见的合成子，其立体选择性的 1,4-官能化可以得到有价值的手性烯丙基衍生物。然而，人们已经将大量的精力集中在离子反应途径上。自由基参与的不对称 1,4-官能化 1,3-烯炔仍然是一个突出的挑战。在此，我们通过双光氧化还原和铬催化描述了 1,3-烯炔的不对称三组分 1,4-二烷基化反应，以提供手性烯醇。该方法具有易得的起始原料、广泛的底物范围、良好的官能团兼容性、高区域选择性以及同时控制轴向和中心手性的特点。机理研究表明，该反应通过自由基参与的氧化还原中性途径进行。
