卡宾
重氮
环丙烷化
环加成
化学
催化作用
对映选择合成
组合化学
药物化学
吲哚试验
有机化学
作者
Ming Bao,Luca De Angelis,Marlyn S. Rada,Mark S. Baird,Hadi D. Arman,Daniel J. Wherritt,Michael P. Doyle
出处
期刊:Chem catalysis
[Elsevier]
日期:2023-10-01
卷期号:3 (10): 100778-100778
被引量:2
标识
DOI:10.1016/j.checat.2023.100778
摘要
The catalytic uses of metal carbenes for addition, insertion, and cycloaddition reactions are dependent on their carbene precursor. The limited methods available for the preparation of diazo esters, which are the most common carbene precursors, restrict their ability to impart structural diversity in metal carbene reactions. Here, we report a new methodology for the preparation of diverse vinyldiazoacetate esters and their effective uses in highly enantiocontrolled cyclopropanation, N–H bond insertion, O–H bond insertion, and [3+2]-cycloaddition reactions. 1,2,3-Triazine 1-oxides with a sp3-C–H bond at the 5-position undergo base-catalyzed Dimroth-type rearrangement to form multiply substituted oximidovinyldiazoacetates in high yields at or below room temperature, and these diverse vinyldiazo compounds undergo catalytic metal carbene transformations to produce oximidovinylcyclopropanes, α-oximidovinyl-α-amino acids, and α-hydroxy acids, as well as tricyclic indole derivatives in high yields and enantioselectivities. The new access to vinyldiazo compounds has applicability to a vast array of metal carbene transformations.
科研通智能强力驱动
Strongly Powered by AbleSci AI