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Copper-catalyzed dehydrogenative γ-C(sp³)-H amination of saturated ketones for synthesis of polysubstituted anilines.

ABSTRACT: Metal-catalyzed β-C-H functionalization of saturated carbonyls via dehydrogenative desaturation proved to be a powerful tool for simplifying synthesis of valuable β-substituted carbonyls. Here, we report a copper-catalyzed dehydrogenative γ-C(sp³)-H amination of saturated ketones that initiates the three-component coupling of saturated ketones, amines and N-substituted maleimides to construct polysubstituted anilines. The protocol presented herein enables both linear and α-branched butanones to couple a wide spectrum of amines and various N-substituted maleimides to produce diverse tetra- or penta-substituted anilines in fair-to-excellent yields with good functional group tolerance. The mechanism studies support that this ketone dehydrogenative γ-C(sp³)-H amination was triggered by the ketone α,β-dehydrogenation desaturation that activates the adjacent γ-C(sp³)-H bond towards functionalization. This α,β-dehydrogenation desaturation-triggered cascade sequence opens up a new avenue to the remote C(sp³)-H functionalization of saturated ketones and has the potential to enable the rapid syntheses of complex compounds from simple starting materials.

SUBMITTER: Hu R

PROVIDER: S-EPMC6695438 | biostudies-literature |

REPOSITORIES: biostudies-literature

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