Switchable Chemoselectivity in 3 + 3 Annulation of β,γ-Unsaturated α-Ketoesters and 1H-Pyrazol-5-amines by Cooperative Acid Catalysis with NiII and InI

The exchange of the metal ion from Ni(II) to In(I) leads to a switch in the chemoselectivity of the [3 + 3] annulation of β,γ-unsaturated α-ketoesters and 1H-pyrazol-5-amines in the presence of phosphoric acid 1, affording functionalized 1H-pyrazolo[3,4-b]pyridines 4 in up to 97% yields and highly enantioselective 4,5-dihydro-1H-pyrazolo[3,4-b]pyridines 5 in up to 92% yield and 99% ee.The exchange of the metal ion from Ni(II) to In(I) leads to a switch in the chemoselectivity of the [3 + 3] annulation of β,γ-unsaturated α-ketoesters and 1H-pyrazol-5-amines in the presence of phosphoric acid 1, affording functionalized 1H-pyrazolo[3,4-b]pyridines 4 in up to 97% yields and highly enantioselective 4,5-dihydro-1H-pyrazolo[3,4-b]pyridines 5 in up to 92% yield and 99% ee.