Cycloaddition Initiated by Ynolates: High-Energy Dianion Equivalents as a Molecular Glue

In this paper, ynolate-initiated cycloaddition (annulation) to form a range of carbocycles and heterocycles is described. Ynolates consist of a ketene anion equivalent, which contains both nucleophilic and electrophilic moieties, and a carbodianion equivalent that achieves double addition. Hence, in addition to the usual [n+2] cycloaddition, ynolates can perform formal [n+1]-type annulations. Their high-energy performance has been demonstrated by their triple addition to arynes to generate triptycenes, in which the C–C triple bond of ynolates is cleaved. The synthetic applications of these methods, including natural products synthesis, are also described.1 Introduction2 Preparation of Ynolates2.1 Double Lithiation2.2 Flow Synthesis2.3 Double Deprotonation3 [2+2] Cycloaddition to C=O Bond3.1 To Aldehydes and Ketones3.2 Sequential Cycloaddition4 [2+2] Cycloaddition to Imino Groups

Recent applications of asymmetric organocatalytic annulation reactions in natural product synthesis

A comprehensive and updated summary of asymmetric organocatalytic annulation reactions is presented; in particular, the applications of these annulation strategies to natural products synthesis are highlighted.

Metal-hydride hydrogen atom transfer (MHAT) reactions in natural products synthesis

Metal-hydride hydrogen atom transfer reaction (MHAT) plays an important role in the field of natural products synthesis. MHAT, as a powerful tool, has been employed by chemists to construct C-C,...

Recent advances in Wacker oxidation: from conventional to modern variants and applications

Recent developments in the well-known Wacker oxidation process from conventional to modern variants and applications to natural products' synthesis are compiled in this review.