钯催化 MIA 引导的苯丙氨酸正交-C-H 烷炔化实验和计算研究

IF 2.8 4区化学 Q1 CHEMISTRY, ORGANIC Asian Journal of Organic Chemistry Pub Date : 2024-07-01 DOI:10.1002/ajoc.202400159

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引用次数: 0

摘要

通过甲氧基亚氨基酰基（MIA）介导的钯催化 C-H 功能化，成功实现了取代苯丙氨酸的直接正炔化。这一创新方案展示了应用多种苯丙氨酸底物的能力，从而高效合成了炔化苄胺衍生物。计算研究进一步发现，氟离子增强了钯(IV)的电正性以及还原消除过渡态中 C1 和 C2 之间的相互作用，从而大大加快了炔化过程中的还原消除步骤。

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Experiment and Computational Study on Pd‐Catalyzed MIA‐Directed Ortho‐C−H Alkynlation of Phenylalanine

The direct ortho‐alkynylation of substituted phenylalanine has been successfully achieved through methoxyiminoacyl (MIA)‐mediated Pd‐catalyzed C−H functionalization. This innovative protocol showcases the ability to apply a diverse range of phenylalanine substrates, resulting in the efficient synthesis of alkynylation benzylamine derivatives with notable effectiveness. Computational investigations further revealed that the fluoride ion enhances the electropositivity of Pd(IV) and the interaction between C1 and C2 within the transition state of the reductive elimination, which significantly expedites the reductive elimination step in the alkynylation process.

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来源期刊

Asian Journal of Organic Chemistry CHEMISTRY, ORGANIC-

CiteScore

4.70

自引率

3.70%

发文量

372

期刊介绍： Organic chemistry is the fundamental science that stands at the heart of chemistry, biology, and materials science. Research in these areas is vigorous and truly international, with three major regions making almost equal contributions: America, Europe and Asia. Asia now has its own top international organic chemistry journal—the Asian Journal of Organic Chemistry (AsianJOC) The AsianJOC is designed to be a top-ranked international research journal and publishes primary research as well as critical secondary information from authors across the world. The journal covers organic chemistry in its entirety. Authors and readers come from academia, the chemical industry, and government laboratories.