中国科学技术大学傅尧研究团队报道了镍催化乙烯基芳烃的α-选择性加氢烷基化反应。相关研究成果于2024年8月12日发表于国际顶尖学术期刊《德国应用化学》。

邻近（杂）芳基的C（sp3）中心广泛存在于生理活性分子中。金属氢化物催化烯烃加氢烷基化是一种有效的形成C（sp3）-C（sp3”键的方法，具有底物来源广泛、反应条件温和、选择性操作简单等优点。然而，乙烯基芳烃的加氢烷基化在底物范围方面受到限制，需要使用活化的烷基卤化物或含有螯合基团的烯烃，这仍然是一个挑战。

在此背景下，研究人员报道了一种通用的氢化镍催化乙烯基芳烃加氢烷基化方案。值得注意的是，该系统能够在无额外配体的条件下实现芳基和杂芳基烯烃的α选择性加氢烷基化，表现出优异的偶联效率和选择性。此外，通过引入手性双恶唑啉配体，实现了乙烯基吡咯的区域和对映选择性加氢烷基化，从而促进了α-支链烷基化吡咯衍生物的合成。

附：英文原文

Title: Nickel-Catalyzed α-selective Hydroalkylation of Vinylarenes

Author: Jia-Wang Wang, Qing-Wei Zhu, Deguang Liu, Pei-Wen Chen, Hong-Zhong Chen, Xi Lu, Yao Fu

Issue&Volume: 2024-08-12

Abstract: C(sp3) centers adjacent to (hetero)aryl groups are widely present in physiologically active molecules. Metal-hydride-catalyzed hydroalkylation of alkenes represents an efficient means of forging C(sp3)-C(sp3) bonds, boasting advantages as a wide source of substrates, mild reaction conditions, and facile selectivity manipulation. Nevertheless, the hydroalkylation of vinylarenes encounters constraints in terms of substrate scope, necessitating the employment of activated alkyl halides or alkenes containing chelating groups, remains a challenge. In this context, we report a general nickel-hydride-catalyzed hydroalkylation protocol for vinylarenes. Remarkably, this system enables α-selective hydroalkylation of both aryl and heteroaryl alkenes under an extra ligand-free condition, demonstrating excellent coupling efficiency and selectivity. Furthermore, through the incorporation of chiral bisoxazoline ligands, we have achieved regio- and enantioselective hydroalkylation of vinylpyrroles, thereby facilitating the synthesis of α-branched alkylated pyrrole derivatives.

DOI: 10.1002/anie.202413074

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202413074