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.

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.

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.].

Recent metal-catalysed approaches for the synthesis of cyclopenta[b]indoles.

The cyclopenta[b]indole scaffold is ubiquitously present in several bioactive natural products and pharmaceutically interesting compounds. Of the numerous methods known for the synthesis of cyclopenta-fused indoles, this review highlights only the metal-catalysed approaches reported from the year 2015 onwards. This review encompasses our own efforts leading to the synthesis of cyclopentannulated indoles, in addition to the seminal contributions of several other researchers.

Synthesis of benzofurans via an acid catalysed transacetalisation/Fries-type O → C rearrangement/Michael addition/ring-opening aromatisation cascade of ß-pyrones.

An unusual and facile approach for the synthesis of 2-benzofuranyl-3-hydroxyacetones from 6-acetoxy-ß-pyrones and phenols is presented. The synthetic sequence involves a cascade transacetalisation, Fries-type O → C rearrangement followed by Michael addition and ring-opening aromatisation. The versatility of this method was further demonstrated via the synthesis of 4,4a-dihydropyrano[3,2-b]benzofuran-3-ones, furo[3,2-c]coumarins, and spiro[benzofuran-2,2'-furan]-4'-ones. The unexpected cascade event would also provide new possible considerations in the ß-pyrone-involved organic synthesis.

Expeditious metal-free access to functionalized polycyclic acetals under mild aqueous conditions.

A facile approach for the synthesis of furopyrans and bicyclic bisacetals under mild aqueous conditions is described. This potentially green, diversity oriented approach involves cascade Michael addition and cycloacetalization of pyranones and 1,3-dicarbonyls. An interesting switch in the product class was observed depending on the type of pyranone employed. Products of type I and II obtained herein are an integral part of several bioactive natural products and medicinally interesting compounds.