Optically pure 1,2-diols are one of the most privileged structural motifs. They are not only frequently found in natural products and drugs, but are also regarded as very useful synthons in organic synthesis. Asymmetric dioxygenation of alkenes could potentially provide a highly efficient and straightforward method for the synthesis of enantioenriched 1,2-diols. Although enantioselective dioxygenations on different alkenes have been studied widely, those on terminal alkenes remain elusive. Herein, we report a Pd(ii)-catalysed enantioselective diacetoxylation of terminal alkenes, including challenging substrates such as 1-propene and 1-butene. Notably, ligand engineering of the simple pyridinyl oxazoline ligand is essential for substantially increasing the catalytic reactivity of Pd(OAc)₂. The method exhibits an exquisite selectivity for terminal alkenes, allowing precise asymmetric diacetoxylation reactions from feedstock alkenes to complex molecules bearing multiple alkenic moieties, which provides rapid and efficient access to various synthetically useful chiral 1,2-diols.

光学纯的 1,2-二醇是最特殊的结构基元之一。它们不仅经常存在于天然产物和药物中，而且被认为是有机合成中非常有用的合成子。烯烃的不对称双氧合可能为合成富含对映体的 1,2-二醇提供一种高效且直接的方法。尽管已经广泛研究了不同烯烃的对映选择性双氧合，但末端烯烃上的对映选择性双氧合仍然难以捉摸。在此，我们报告了 Pd( ii ) 催化的末端烯烃的对映选择性双乙酰氧基化，包括具有挑战性的底物，例如 1-丙烯和 1-丁烯。值得注意的是，简单的吡啶基恶唑啉配体的配体工程对于显着提高 Pd(OAc) _{2的催化活性至关重要}. 该方法对末端烯烃表现出极佳的选择性，允许从原料烯烃到带有多个烯烃部分的复杂分子的精确不对称二乙酰氧基化反应，从而快速有效地获得各种合成有用的手性 1,2-二醇。