Propargylation of nitroalkanes via the copper-catalyzed cross coupling
Date
2019
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Publisher
University of Delaware
Abstract
Chapter 1 begins with a brief introduction of the importance of nitroalkanes in organic synthesis. Nitroalkanes can easily be converted into different functional groups, such as carbonyls, oximes, amines, or corresponding alkanes. The nitronate anions can participate in a variety of reactions, including Henry reaction, Michael reaction, nitro-Mannich reaction, Tsuji-Trost allylation or Buchwald arylation, etc. Despite their exceptional ability to generate new C—C bonds, a simple reaction between nitroalkanes and alkyl halides had proved challenging due to an undesired O-alkylation. Our group has successfully used transition metal catalysis to perform C-alkylation of nitroalkanes. ☐ Chapter 2 describes the discovery of the synthesis of homopropargylic nitroalkanes (β-nitroalkynes) from propargylic halides via a copper catalysis and its synthetic application. First, conventional methods and their limitations to synthesize β-nitroalkynes are reviewed. Then, optimization of reaction conditions is described: by using CuBr as catalyst and N,N-diisopropylethane- 1,2-diamine as ligand, β-nitroalkynes are generated in high yield and the formation of β-nitroallenes is suppressed. Finally, we investigated on the substrate scope and concluded that this protocol tolerated a wide scope of functional groups.