Seoyeon Kim, Da Seul Lee, Naeem Iqbal, Jaehan Bae, Ho Seong Hwang, Doohyun Baek, Sukwon Hong, Eun Jin Cho
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引用次数: 0
Abstract
We report a nickel-catalyzed approach for the efficient synthesis of tetrasubstituted allenes from tertiary propargylic substrates, which remains a significant challenge due to competing substitution reactions and regioselectivity issues. Leveraging an optimized Ni-PˆN catalytic system, the notable non-covalent interactions (NCIs) overcome inherent stability issues and achieve regio- and stereoselectivity. Through a combination of experimental and computational analyses, we elucidate the stabilization mechanisms of the critical β-[Ni]-alkenyl intermediate from the reactions of arylated propargyl substrates. Our findings demonstrate that NCIs, in particular hydrogen bonding interactions between a unique free amino-type PˆN ligand and the substrate, are key to achieving precise control over the process. The efficiency of the process is greatly influenced by subtle differences in the ligand system through control of the bite angle and coordination length in the key nickel complex intermediates.
期刊介绍:
Chem Catalysis is a monthly journal that publishes innovative research on fundamental and applied catalysis, providing a platform for researchers across chemistry, chemical engineering, and related fields. It serves as a premier resource for scientists and engineers in academia and industry, covering heterogeneous, homogeneous, and biocatalysis. Emphasizing transformative methods and technologies, the journal aims to advance understanding, introduce novel catalysts, and connect fundamental insights to real-world applications for societal benefit.