Morita-Baylis-Hillman Spirannulation under Phosphine- and Anion-Binding Catalysis.

We introduce an advancement in Morita-Baylis-Hillman (MBH) chemistry that provides access to α-spirannulated enones. The treatment of enone-tethered azaarenium salts with catalytic amounts of organophosphines provides spiroindenyl dihydropyridines. It represents the α-spirannulation of enones via an intramolecular MBH (IMBH) reaction utilizing dual phosphine- and anion-binding catalysis. The IMBH adducts were subjected to several post-synthetic modifications to access highly functionalized molecules.

An interrupted Corey-Chaykovsky reaction of designed azaarenium salts: synthesis of complex polycyclic spiro- and fused cyclopropanoids.

Simultaneous dearomatizing spirannulation of pyridinium salts is still in its infancy. Here, we present an organized skeletal remodeling of designed pyridinium salts by utilizing an interrupted Corey-Chaykovsky reaction to access unprecedented and structurally intriguing molecular architectures such as the vicinal bis-spirocyclic indanones and spirannulated benzocycloheptanones. This hybrid strategy rationally merges the nucleophilic features of sulfur ylides with the electrophilic pyridinium salts to achieve the regio- and stereoselective synthesis of new classes of cyclopropanoids. The plausible mechanistic pathways were derived from experimental results and control experiments.

Pd-Catalyzed Nazarov-Type Cyclization: Application in the Total Synthesis of ß-Diasarone and Other Complex Cyclopentanoids.

We describe the palladium-catalyzed Nazarov-type cyclization of easily accessible (hetero)arylallyl acetates to pentannulated (hetero)arenes. This method provides ready access to various types of bi-, tri-, tetra-, and pentacyclic cyclopentanoids under neutral conditions. The synthetic utility is further demonstrated in the first total synthesis of ß-diasarone and several other complex cyclopentanoids relevant to medicinal chemistry and materials science.

Hypothesis-Driven Palladium-Catalyzed Transformations for the Construction of New Molecular Architectures.

The development of new synthetic protocols to access diverse molecular scaffolds from readily available starting compounds is of significance in both academia and industry. Towards this, the catalysis by transition metals has been employed as a powerful tool to access molecules with broad structural and functional diversity. An overview of the recent literature manifested the tremendous potential of transition metal-catalyzed processes in advancing organic synthesis in a new direction. This account compiles new conceptual advancements in the palladium-catalyzed Alder-ene type cycloisomerization reactions, C-H functionalizations, and one-pot multicatalytic processes, which have become essential tools to access new classes of molecules.

Palladium-catalysed 5-endo-trig allylic (hetero)arylation.

A palladium-catalysed intramolecular allylic (hetero)arylation strategy for the synthesis of fused cyclopentenes incorporated with all-carbon quaternary and spiro centres is described. The method is straightforward, shows broad scope, proceeds in synthetically useful yields, and provides a rare means to construct complex cyclopentanoids. The reaction is believed to involve a kinetically unfavourable 5-endo-trig carbocyclisation of the tethered (π-allyl)palladium system. Further, this method was successfully applied as the key step in the total synthesis of diterpene natural products taiwaniaquinone H and dichroanone.

Correction: Palladium-catalysed 5-endo-trig allylic (hetero)arylation.

[This corrects the article DOI: 10.1039/D0SC01932A.].

Palladium-Catalyzed Intramolecular Trost-Oppolzer-Type Alder-Ene Reaction of Dienyl Acetates to Cyclopentadienes.

A new approach to the synthesis of highly substituted cyclopentadienes, indenes, and cyclopentene-fused heteroarenes by means of the Pd-catalyzed Trost-Oppolzer-type intramolecular Alder-ene reaction of 2,4-pentadienyl acetates is described. This unprecedented transformation combines the electrophilic features of the Tsuji-Trost reaction with the nucleophilic features of the Alder-ene reaction. The overall outcome can be perceived as a hitherto unknown "acid-free" iso-Nazarov-type cyclization. The versatility of this strategy was further demonstrated by the formal synthesis of paucifloral F, a resveratrol-based natural product.