Catalytic Enantioselective Reactions of Biomass-Derived Furans

Dong Guk Nam,Do Hyun Ryu,Jung Woon Yang

doi:10.5772/intechopen.101827

Abstract

In this chapter, recent developments with regard to catalytic enantioselective reactions of furans, derived from biomass such as unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and furfural are described. Although several review articles have dealt with the Diels-Alder reactions of furans, there have been no articles highlighting enantioselective versions. The resulting products derived from the catalytic enantioselective reaction of furan are often found as core structures in natural products and pharmaceuticals with important pharmacological activities. After recognizing the valuable skeleton of chiral furan derivatives, numerous attempts have been made to synthesize them by utilizing enantioselective cycloaddition reactions, Friedel-Crafts reactions, and nucleophilic addition reactions. Enantioselective cyclization reactions using furans as the 4π diene component provided chiral dihydrofuran derivatives. On the other hand, Friedel-Crafts and nucleophilic addition reactions served various furan derivatives with a chiral carbon atom in the α-position.

Highlights

Furfural and 5-hydroxymethylfurfural (HMF) have received significant attention as promising platform chemicals due to their versatile utility in the synthesis of various commodity chemicals and fuels [1–3]
Since aromatic heterocycle furans are present in a variety of chiral natural products, pharmaceuticals, and other intermediates, a plethora of enantioselective methodologies has been developed for the synthetic community [7–9]
The important strategies are given as follows—(i) enantioselective cyclization reactions including cycloadditions using furans as the 4π diene component and cyclopropanation between furan and diazoester to obtain various valuable chiral synthons (Section 2); (ii) enantioselective Friedel-Crafts cycloadditions for the fabrication of carboncarbon bonds between furans and electron-deficient alkenes, yielding chiral centers at the α- or β-position of furans (Section 3); (iii) various enantioselective nucleophilic addition reactions of furfural as an electrophile for the construction of chiral

Summary

Introduction

Furfural and 5-hydroxymethylfurfural (HMF) have received significant attention as promising platform chemicals due to their versatile utility in the synthesis of various commodity chemicals and fuels [1–3]. These platform chemicals can be transformed into value-added chemicals, such as 2-methylfuran, 2,5dimethylfuran, and other furans via chemical conversions or fermentation [4–6]. Since aromatic heterocycle furans are present in a variety of chiral natural products, pharmaceuticals, and other intermediates, a plethora of enantioselective methodologies has been developed for the synthetic community [7–9]. Furans and Furan Derivatives - Recent Advances and Applications hydroxyl functional groups (Section 4). This chapter is divided into three sections

Catalytic asymmetric cyclization reactions of furans

Cu or Pd-catalyzed enantioselective Diels-Alder reactions with furans

Catalytic asymmetric Friedel-Crafts reactions of furans

Various catalytic asymmetric nucleophilic addition reactions of furfural

Findings

Conclusion