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Palladium-Catalyzed Annulations of Strained Cyclic Allenes
2021-06-22 10:08

美国加州大学洛杉矶分校Neil K. Garg小组最新研究提出了钯催化张力环烯的环化反应。该项研究成果发表在2021年6月18日出版的《美国化学会杂志》上。

该课题组人员报道了钯催化原位生成的张力环烯环化反应。该方法采用卤化芳基和环烯前体作为反应体,用以生成融合杂环产品。环化通过形成两个新键和一个sp3中心来进行。

此外,该方法的非对映和对映选择性变体都得到了验证,后者最终使复杂六环产物的快速对映选择性合成成为可能。利用过渡金属催化拦截环烯的研究背离了以往更常见的依赖亲核试剂或环加成伴体捕获环烯的模式。因此,本研究有望推动策略性结合过渡金属催化和瞬态张力中间体化学实现合成复杂架构反应的发展。

附:英文原文

Title: Palladium-Catalyzed Annulations of Strained Cyclic Allenes

Author: Andrew V. Kelleghan, Dominick C. Witkowski, Matthew S. McVeigh, Neil K. Garg

Issue&Volume: June 18, 2021

Abstract: We report Pd-catalyzed annulations of in situ generated strained cyclic allenes. This methodology employs aryl halides and cyclic allene precursors as the reaction partners in order to generate fused heterocyclic products. The annulation proceeds via the formation of two new bonds and an sp3 center. Moreover, both diastereo- and enantioselective variants of this methodology are validated, with the latter ultimately enabling the rapid enantioselective synthesis of a complex hexacyclic product. Studies leveraging transition metal catalysis to intercept cyclic allenes represent a departure from the more common, historical modes of cyclic allene trapping that rely on nucleophiles or cycloaddition partners. As such, this study is expected to fuel the development of reactions that strategically merge transition metal catalysis and transient strained intermediate chemistry for the synthesis of complex scaffolds.

DOI: 10.1021/jacs.1c04896

Source: https://pubs.acs.org/doi/10.1021/jacs.1c04896

 

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