Study of Enantioselective Catalysis of Nitroso-Diels-Alder Reaction on Solid Support

Abstract

Nitroso-Diels-Alder (NDA) reaction is used as a tool for the synthesis of 3,6-dihydro-1,2-oxazine derivatives, which are important intermediates in the synthesis of natural products and biologically active compounds. In this work, we investigated the enantioselective version of this reaction on a solid support.We studied various catalysts, concentrations, temperatures and solvents and compared them with the best conditions reported for solution-phase chemistry. The best conditions were also applied to other 1,2-oxazine derivatives.

Valence-isomer selective cycloaddition reaction to synthesize functionalized carbocycles

“…Previous studies used nitroso compounds as dienophiles in (4 + 2)-cycloadditions 36 , 37 , 38 , 39 , 40 , even in reactions with CHTs 41 . The (6 + 2)cycloaddition involving nitroso compounds remains elusive (up to 35% yield 42,43 , up to 49% ee 44 ), and no detailed mechanistic studies have been reported. In the reaction with benzyne species, the (4 + 2)cycloaddition proceeded selectively toward NCD as another valence isomeric form.…”

Valence-isomer selective cycloaddition reaction of cycloheptatrienes-norcaradienes

“…Previous studies used nitroso compounds as dienophiles in [4 + 2]-cycloadditions [40][41][42][43][44] , even in reactions with CHTs 45 . The [6 + 2]-cycloaddition involving nitroso compounds remains elusive (up to 35% yield 46,47 , up to 49% ee 48 ), and no detailed mechanistic studies have been reported. In the reaction with benzyne species, the [4 + 2]-cycloaddition proceeded selectively toward NCD as another valence isomeric form.…”