Cascade Ring-Opening/Cyclization Reaction of Spiro(nitrocyclopropane)oxindoles with Huisgen Zwitterions and Synthesis of Pyrazolo[3,4-b]indoles.

Herein, we report a ring-opening/cyclization cascade reaction of spiro(nitrocyclopropane)oxindoles with in situ generated Huisgen zwitterions (HZs) from PPh3 and azodicarboxylates. This reaction provides an array of polyfunctionalized pyrazolo[3,4-b]indole derivatives in moderate-to-excellent yields and generally high stereoselectivities with a broad substrate scope. The annulation products obtained from di-tert-butyl azodicarboxylates can be readily transformed into aromatic-substituted pyrazolo[3,4-b]indoles in moderate yields upon treatment with trifluoroacetic acid, thus providing a new entry to this fused heterocycle skeleton. In terms of nitro-substituted donor-acceptor cyclopropane, this work significantly broadens the substrate scope for the annulation reaction of nitrocyclopropanes and HZs. The dual roles of the oxindole moiety in the ring opening of cyclopropane and a plausible mechanism for the cascade reaction are also discussed.

Enantioselective Synthesis of Quaternary Oxindoles: Desymmetrizing Staudinger-Aza-Wittig Reaction Enabled by a Bespoke HypPhos Oxide Catalyst.

This paper describes a catalytic asymmetric Staudinger-aza-Wittig reaction of (o-azidoaryl)malonates, allowing access to chiral quaternary oxindoles through phosphine oxide catalysis. We designed a novel HypPhos oxide catalyst to enable the desymmetrizing Staudinger-aza-Wittig reaction through the PIII/PV═O redox cycle in the presence of a silane reductant and an IrI-based Lewis acid. The reaction occurs under mild conditions, with good functional group tolerance, a wide substrate scope, and excellent enantioselectivity. Density functional theory revealed that the enantioselectivity in the desymmetrizing reaction arose from the cooperative effects of the IrI species and the HypPhos catalyst. The utility of this methodology is demonstrated by the (formal) syntheses of seven alkaloid targets: (-)-gliocladin C, (-)-coerulescine, (-)-horsfiline, (+)-deoxyeseroline, (+)-esermethole, (+)-physostigmine, and (+)-physovenine.

Phosphine-catalyzed [4+1] annulation of 1,3-(aza)dienes with maleimides: highly efficient construction of azaspiro[4.4]nonenes.

Phosphine-catalyzed [4+1] annulation of electron-deficient 1,3-dienes or 1,3-azadienes with maleimides has been successfully developed under very mild conditions, providing a convenient and highly efficient method for constructing 2-azaspiro[4.4]nonenes and 1,7-diazaspiro[4.4]nonenes. This reaction represents the first example of [4+1] cyclization between electron-deficient 4π-conjugated systems and non-allylic phosphorus ylides.