2,8-Diheterobicyclo[3.2.1]octane Ring Systems: Natural Occurrence, Synthesis and Properties

Abstract

This account describes the developments on the synthesis and reactivity of functionalized 2,8-diheterobicyclo[3.2.1]octanes. The continued interest in the chemistry of these compounds is mainly due to their abundance in Nature, being at the core of numerous families of biologically active natural products, and also as a result of their versatile reactivity, which makes them very useful building blocks with considerable impact in modern organic synthesis. The present article is aimed toward providing a comprehensive coverage of the literature on these heterocyclic scaffolds, including our own contributions, and has been organized according to the nature of the heteroatom embedded in the 2,8-bicyclo[3.2.1]octane framework. 1 Introduction 2 2,8-Dioxabicyclo[3.2.1]octane Systems 2.1 Natural Products 2.1.1 Marine Origin: Pectenotoxins, Saliniketals 2.1.2 Terrestrial Origin: Fungus (Squalestatins), Plants 2.2 Synthetic Products 3 2-Aza-8-oxabicyclo[3.2.1]octane Systems 3.1 Cyclonucleotides 3.2 Diazaimide Derivatives 3.3 Systems with a 1,3-Oxazepane Core 3.4 2-Aza-8-oxabicyclo[3.2.1]octanes Fused with Aromatic Rings 3.5 Other Bicyclic Systems 4 2-Thia-8-oxabicyclo[3.2.1]octane Systems 4.1 From Sugars 4.2 Compounds for Asymmetric Epoxidation 4.3 Compounds from Photoreactions of Thioketones 5 2-Oxa-8-azabicyclo[3.2.1]octane Systems 5.1 Natural Products: <i>Kopsia</i> Alkaloids 5.2 Synthetic Products 6 2,8-Diazabicyclo[3.2.1]octane Systems 6.1 Natural Products: Albomitomicyn 6.2 Synthetic Products: Epibatidine Analogues 7 2-Thia-8-azabicyclo[3.2.1]octane Systems 7.1 Natural Products: Diketopiperazines 7.2 Synthetic Products 8 Conclusions