Amine compounds are ubiquitous in natural products and biologically active molecules as well as valuable intermediates in organic synthesis and medicinal chemistry. Among numerous methodologies for synthesis of amines, the direct addition of an N-H bond across a multiple C-C bond is one of the most efficient and atom economic routes. Transition-metal catalysts in this amination have played a significant role in promoting its reactivity and controlling regio-and stereoselectivities. In this study, we developed new copper catalytic systems for aza-Michael addition of (hetero)arylamines to α,β-unsaturated carbonyls and for intermolecular anti-Markovnikov hydroamination of (hetero)arylamines with vinylrenes. The low cost and easy-to-handle Cu salt, readily available phosphine or imidazolium salts, and KOt-Bu were used to generate a Cu amido complex in situ as the catalytic species. Using the catalytic system, we performed regioselective amine addition to disubstituted-α,β-unsaturated ketones and terminal or internal NO2-substituted vinylarenes, affording new versatile amine products in good to excellent yields. In addition, we applied our methodology to synthesize a variety of 3-carbonyl-2-substituted quinolin-4(1H)-ones, which are potential intermediates for pharmaceuticals.

Cu-catalyzed amination of (hetero)arylamines to disubstituted olefins

2019 Fall National Meeting

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