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Rhodium-Catalyzed Anti-Markovnikov Hydroamination of Aliphatic and Aromatic Terminal Alkynes with Aliphatic Primary Amines

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2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis

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Summary: Utilizing 8-quinolinolato rhodium catalysts and CsF, the coupling of alkylacetylenes with secondary amines in both 2:1 and 1:1 ratios was achieved. The solvent choice can switch the selectivity between 2:1 and 1:1 ratios, leading to different products under different reaction conditions.Additionally, anti-Markovnikov hydroamination reactions in toluene resulted in 1:1 coupling products under relatively mild conditions.

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