Jia Xue-Gong, Yao Qi-Wei, Shu Xing-Zhong
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China.
J Am Chem Soc. 2022 Aug 3;144(30):13461-13467. doi: 10.1021/jacs.2c05523. Epub 2022 Jul 25.
Asymmetric cross-electrophile difunctionalization of tethered alkenes has become a powerful tool for the production of chiral cyclic scaffolds; however, the current studies all focus on carbocyclization reactions. Herein, we report an -cyclization-alkylation reaction and thus showcase the potential of heterocyclization for accessing new enantioenriched cyclic architectures. This work establishes a new approach for enantioselective aza-Heck cyclization/cross-coupling sequence, which remains a long-standing unsolved challenge for the synthetic community. The reaction proceeds with primary, secondary, and a few tertiary alkyl iodides, and the use of newly defined ligands gave highly enantioenriched pyrrolines with improved molecular diversity under mild conditions. The presence of imine functionality allows for further structural variations.
tethered烯烃的不对称交叉亲电双官能化已成为构建手性环状骨架的有力工具；然而，目前的研究都集中在碳环化反应上。在此，我们报道了一种氮环化-烷基化反应，从而展示了杂环化在构建新的对映体富集环状结构方面的潜力。这项工作建立了一种对映选择性氮杂Heck环化/交叉偶联序列的新方法，这仍然是合成领域长期未解决的挑战。该反应可与伯、仲和一些叔烷基碘化物进行，使用新定义的配体在温和条件下可得到具有更高分子多样性的高对映体富集的吡咯啉。亚胺官能团的存在允许进一步的结构变化。
