A series of compounds featuring a novel bispiro­[indanedione-oxindole-cyclopropane] moiety have been synthesized through a squaramide-catalyzed [2+1] cycloaddition reaction. The tandem Michael-alkylation reaction of 2-arylidene-1,3-indanediones with 3-bromooxindoles furnished the cycloadducts in high yields with excellent diastereo- and enantioselectivities. The ammonium ylide in the catalytic process, as a key intermediate, was revealed by the high-resolution mass spectrometry study.

The first enantioselective formal (3 + 2) cyclocondensation involving α,β-unsaturated pyrazoleamides as 3-carbon partners was accomplished in a stepwise fashion. The stepwise esterification/Michael addition sequence is promoted by Zn(OTf) 2 and quinine-squaramide derivative, respectively. The protocol enables access to spiro-fused pentacyclic spirooxindoles from coumarin-3-formylpyrazoles and 3-hydroxyoxindoles in good to satisfactory overall yields (up to 91%) with excellent dr (all cases >20:1 dr) and high ee values (up to 99%). Mechanistic investigations contributed to shedding light on the enantioselective event of the process.

C13H7BrN2O3, triclinic, P 1 ‾ $\overline{1}$ (no. 2), a = 7.2968(6) Å, b = 7.6743(6) Å, c = 11.5698(12) Å, α = 77.255(8)°, β = 73.573(8)°, γ = 73.509(7)°, V = 588.90(10) Å3, Z = 2, R gt (F) = 0.0459, wR ref (F 2) = 0.1089, T = 220 K.