【Gong Chen and Gang He's Group 】Benzazetidine synthesis via palladium-catalysed intramolecular C−H amination-元素有机化学国家重点实验室

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【Gong Chen and Gang He's Group 】Benzazetidine synthesis via palladium-catalysed intramolecular C−H amination

Source：SKLEOC Date：2016/10/11

Small-sized N-heterocycles are important structures in organic synthesis and medicinal chemistry. Palladium-catalysed intramolecular aminations of the C−H bonds of unfunctionalized amine precursors have recently emerged as an attractive new method for N-heterocycle synthesis. However, the way to control the reactivity of high-valent Pd intermediates to form the desired C−N cyclized products selectively remains poorly addressed. Prof. Gong Chen and Prof. Gang He have reported a strategy to control the reductive elimination (RE) pathways in high-valent Pd catalysis and apply this strategy to achieve the synthesis of highly strained four-membered benzazetidines via the Pd-catalysed intramolecular C−H amination of N-benzyl picolinamides. These reactions represent the first practical synthetic method for benzazetidines and enable access to a range of complex benzazetidines from easily obtainable starting materials. The use of a newly designed phenyliodonium dimethylmalonate reagent is critical, as oxidation of Pd(II) palladacycles with this reagent favours a kinetically controlled C−N RE pathway to give strained ring-closed products.

Link: ht tp ://www.nature.com/nchem/journal/vaop/ncurrent/full/nchem.2585.html.

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