An unprecedented organocatalytic asymmetric Michael/cyclization cascade reaction of 3-isothiocyanato oxindoles and 3-nitroindoles has been disclosed. A wide range of enantioenriched polycyclic spirooxindoles, containing three contiguous chiral centers with two of them having quaternary stereocenters, could be smoothly obtained with satisfactory results (up to 99% yield, >99:1 dr, and 96% ee). This method is very promising because the reaction is scalable, and the versatile transformations of the products into other spirocyclic oxindoles are also feasible. E xploring efficient strategies for the construction heterocyclic compounds with rich structural diversity and complexity is a continuing challenge in synthetic chemistry. The spirooxindole skeletons in particular have captured tremendous attention among synthetic and medicinal chemists, due to their prevalence in a broad range of natural and unnatural biologically active products, as well as pharmaceutically important compounds. 1 Over the past several years, we have witnessed rapid progress in the development of creative methodologies for the generation of diverse spirooxindole molecules. 2 Specifically, numerous multifunctional polycyclic spirooxindoles, featuring structural complexity and well-defined three-dimensional architecture, have been demonstrated to correlate with a wide spectrum of biological properties and pharmacological activities (Figure 1). 3 Various synthetic methods for producing functionalized spirooxindole derivatives containing a polycyclic skeleton in asymmetric catalysis have been reported. 4 Despite the substantial advances made thus far, taking into account the importance of the natural-product-like spirocyclic oxindoles in pharmaceutical science and as promising candidates for drug discovery, the development of novel approaches for the efficient synthesis of polyfunctionalized spirooxindoles is in demand.Since we initially employed 3-isothiocyanato oxindoles as nucleophiles in catalytic asymmetric synthesis, 5 many studies have documented the stereoselective construction of structurally diverse spirocyclic oxindoles using 3-isothiocyanato oxindoles as powerful and versatile precursors via cascade reaction. 6,7 Notably, 3-isothiocyanato oxindoles can easily undergo Michael/cyclization cascade reactions with some electrondeficient alkenes. 6 In addition, the indoles, bearing two electron-withdrawing substitutions at the N1-and C3-positon, have been recognized as a class of electron-deficient alkene reagents. 8 These indoles possess special reaction features; that is, they are readily attacked by nucleophiles at the C2-position and sequentially react with electrophiles at the C3-position (Scheme 1A). We noticed that 3-nitroindoles, 8 a class of potentially promising electrophilic alkenes, had barely been explored in the field of catalytic asymmetric synthesis. 9 In this context, as our continuous interest in developing new synthetic methods for the

The first organocatalyzed asymmetric dearomative cycloaddition between 2-nitrobenzofurans and isatin-derived Morita–Baylis–Hillman carbonates has been developed. Using a modified cinchona alkaloid as the catalyst, a series of structurally diverse cyclopenta­[b]­benzofuran derivatives with three contiguous stereocenters, including a spiro-quaternary chiral center, could be smoothly obtained in excellent results (all cases >20:1 dr, up to 99% yield and 98% ee). The utility of this method was showcased by the versatile transformations of the product.