The enantioselective aza-Friedel–Crafts reaction is one of the most straightforward and efficient strategies for constructing a new carbon-carbon bond bearing quaternary stereocenter in organic synthesis, but the catalytic asymmetric aza-...

The β-C-H functionalization of amines is one of the most powerful tools for the synthesis of saturated nitrogen-containing heterocycles in organic synthesis. However, the β-C–H functionalization of amines via redox-neutral...

A chiral phosphoric acid‐catalyzed enantioselective aza‐Friedel–Crafts reaction of 5‐aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation of pyrazole‐based C2‐quaternary indolin‐3‐ones with high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis of the 5‐aminopyrazole‐based C2‐quaternary indolin‐3‐ones was performed, with no decrease in the yield and enantioselectivity.

The enantioselective aza-MBH reaction is an efficient strategy for constructing novel carbon–carbon bonds, providing access to multitudinous chiral densely functionalized MBH products. However, the enantioselective aza-MBH reaction of cyclic-ketimines that would generate a versatile synthon is still missing and challenging. Herein, we developed a challenging direct organocatalytic asymmetric aza-MBH reaction involving cyclic ketimines attached to a neutral functional group. Moreover, the α,β-unsaturated γ-butyrolactam was utilized as a rare nucleophile alkene in this work. The reactions provide enantiomerically enriched 2-alkenyl-2-phenyl-1,2-dihydro-3H-indol-3-ones, bearing with a tetra-substituted stereogenic center. Moreover, this reaction features high α-selectivities, high enantioselectivities (up to 99% ee), and good yields (up to 80%).

A Friedel–Crafts reaction of indolizines with 2‐aryl‐3H‐indol‐3‐ones catalyzed by B(C6F5)3 is described. This protocol gives access to indolizine derivatives that are valuable building blocks in synthetic and pharmaceutical chemistry. The reaction proceeds under mild conditions, affording various C2‐quaternary indolin‐3‐ones based on indolizine with high yields and regioselectivities. Moreover, the synthetic transformations of the target products were realized by N‐methylation and trifluoromethane sulfonation.