湖南大学赵万祥团队报道了烯基硼酸盐的不对称氧化乳糖化反应。相关研究成果于2022年8月23日发表于国际顶尖学术期刊《德国应用化学》。

CB键的氧化广泛用于有机合成、材料科学和化学生物学。然而，这些氧化通常限于C（sp3）B和C（sp2）B键。C（sp）B键氧化很少发生。

该文提出了一种通过氧化烯炔基硼酸酯制备γ-内酯的新策略。该过程依次包括C（sp）B键氧化、CC双键环氧化和乳糖化。该方案有效地提供了多种天然产物和生物活性分子中普遍存在的γ-内酯和不饱和丁烯内酯。最重要的是，还实现了烯炔基硼酸酯的不对称氧化内酯化，高对映选择性和非对映选择性提供了手性γ-内酯。γ-内酯的多功能转化和普遍性说明了该策略在复杂分子的构建和后期功能化中的重要性。

附：英文原文

Title: Asymmetric Oxidative Lactonization of Enynyl Boronates

Author: Kezhuo Zhang, Chenchen Li, Yining Jia, Wanxiang Zhao

Issue&Volume: 2022-08-23

Abstract: Oxidation of CB bonds is extensively used in organic synthesis, materials science, and chemically biology. However, these oxidations is usually limited to the oxidation of C(sp3)B and C(sp2)B bonds. The C(sp)B bond oxidation is rarely developed. Herein we present a novel strategy for the preparation of γ-lactones via the oxidation of enynyl boronates. This process successively involves the C(sp)B bond oxidation, the epoxidation of CC double bond and the lactonization. This protocol provided various γ-lactones and unsaturated butenolides efficiently that are prevalent in numerous nature products and bioactive molecules. Most importantly, asymmetric oxidative lactonization of enynyl boronates was also achieved, providing chiral γ-lactones in high enantioselectivitis and diastereoselectivities. The versatile transformations and ubiquity of γ-lactones shed light on the importance of this strategy in the construction and late-stage functionalization of complex molecules.

DOI: 10.1002/anie.202209004

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202209004