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.
Keywords
- enantioselective
- cycloaddition
- Diels-Alder
- Friedel-Crafts
- furan
- nucleophilic addition
1. 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, 2, 3]. These platform chemicals can be easily transformed into value-added chemicals, such as 2-methylfuran, 2,5-dimethylfuran, and other furans via chemical conversions or fermentation [4, 5, 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, 8, 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 carbon-carbon 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 hydroxyl functional groups (Section 4). Thus, this chapter is divided into three sections.
2. Catalytic asymmetric cyclization reactions of furans
Since the first cyclopropanation between unsubstituted furan and chlorodiazopropene was reported by de Meujere and Kositkov in 1991, reactions using unfunctionalized furan have emerged as a challenging area in organic chemistry [10]. In most cases, numerous reports have utilized substituted furan at the 2- or 3-positions. However, biomass-derived furan such as normal furan or methyl-substituted furans are generally held to be poor dienes in Diels-Alder reactions and have poor reactivity for cyclization as well as cyclopropanation. Therefore, it has been difficult to develop such reactions with simple furan, and extending it to the catalytic enantioselective version was extremely difficult. Since the discovery of an enantioselective furan Diels-Alder reaction in 1997 by the Evans group [11], some progress in this area has been achieved. The aim of this chapter is to mainly discuss the catalytic enantioselective reaction of simple furans for Diels-Alder reaction, [4 + 3] cyclization, and cyclopropanation. The reaction of functionalized and substituted furan will not be included here.
2.1 Cu or Pd-catalyzed enantioselective Diels-Alder reactions with furans
The first highly enantioselective catalytic Diels-Alder reaction using an unsubstituted furan reactant was accomplished by the Evans group in 1997 [12, 13]. They utilized a bisoxazoline-copper complex
The Diels-Alder reaction between acrylamide
2.2 Oxazaborolidium-catalyzed enantioselective Diels-Alder reactions with furans
A few examples of catalytic asymmetric Diels-Alder reaction of unsubstituted furans have been reported. Corey, Ryu, and coworkers successfully reported the Diels-Alder reaction between furan
In 2011, Shibatomi and coworkers accomplished chiral oxazaborolidine
Corey and coworkers reported asymmetric Diels-Alder reactions of di-substituted furans
Occasionally, the catalytic system comprising a chiral
In 2010, Corey and coworkers reported a catalytic asymmetric Diels-Alder reaction by employing an allenic ester
The usefulness of the Diels-Alder cycloadduct
An alternative organocatalytic Diels-Alder reaction of furan
2.3 Enantioselective [4 + 3] cyclization (or annulation) reactions with furans
The [4 + 3]-annulation consisting of the tandem cyclopropanation/Cope rearrangement of furan is a useful and predictable tool for the stereoselective synthesis of seven-membered rings. Asymmetric synthesis of 8-oxabicyclo[3.2.1]octene derivatives (
In 2008, the same group described the Tetrakis[(
In 2017, Vicario and coworkers reported that chiral 1,1-binaphthol (BINOL)-based Brønsted acid
In 2017, Jacobsen and coworkers reported that H-bond donors such as chiral squaramide
2.4 Enantioselective cyclopropanation reactions with furans
Reactions of furans with carbenoids led to cyclized reactions, such as cyclopropanation. Additionally, a cyclopropanation reaction could be performed through the reaction of furan and diazoacetate under a metal catalyst. Reiser and coworkers reported the enantioselective cyclopropanation of furans using a copper catalyst, however, the reaction was achieved when the furan was substituted with ester groups at the 2- or 3-position [27]. To solve this problem, Davies and coworkers designed the catalytic system using dirhodium catalyst. When simple furan and aryl diazoester was subjected to the rhodium-catalyzed enantioselective cyclopropanation reaction, both cycloadduct product
3. Catalytic asymmetric Friedel-Crafts reactions of furans
One of the most efficient methods for the synthesis of chiral heteroaromatic compounds with a stereogenic center in the benzylic position is the Friedel-Crafts reaction between carbonyl compounds and electron-deficient alkenes [29]. This field of chemistry has been intensely explored since around 2000, and interest in this field is still growing. Most catalytic enantioselective Friedel-Crafts reactions can be utilized with electron-rich aromatic and heteroaromatic compounds, such as aniline and indole derivatives. However, reports with regard to the use of furans for this study are still scarce due to the relative instability and reduced nucleophilicity of furans compared to indoles and pyrroles [30]. In particular, catalytic enantioselective versions of the Friedel-Crafts reaction with biomass-derived furans as well as normal furan are much less developed than other aromatics.
The first catalytic enantioselective Friedel-Crafts reaction using biomass-derived furan was accomplished by the Jørgensen group in 2000 [31]. Only methyl or trimethylsilyl-substituted furans
One year later, in 2001, the same group described an enantioselective Friedel-Crafts reaction of normal furan or biomass-derived furans
In 2009, Yamazaki and coworkers utilized chiral
Another attempt with regard to the asymmetric Friedel-Crafts reaction of furans
A few years later, in 2008, the same group successfully performed catalytic enantioselective Friedel-Crafts reaction between furans
Cationic square planar metal complexes [M(diphosphine)]2+, where M = Pt, Pd, Ni)] have emerged as an alternative class of Lewis acid catalysts such as Cu-bisoxazolines (Box), Ti-BINOL, and Co-salen due to the following unique characteristics—(i) well-defined coordination geometries to help control the stereochemical environment; (ii) high carbophilicity; and (iii) tunable electronic properties for enhancing Lewis acidity [36]. Mehdi-Zodeh and coworkers introduced cationic square planar-platinum or palladium metal complexes as Lewis acid catalysts into the Friedel-Crafts reaction between biomass-derived furans
The first enantioselective organocatalytic Friedel-Crafts reaction with biomass-derived furan
In 2010, Harada and coworker reported an organocatalytic Friedel-Crafts reaction between furans
The highly enantioselective organocatalytic Friedel-Crafts reaction with biomass-derived furan
4. Various catalytic asymmetric nucleophilic addition reactions of furfural
Asymmetric nucleophilic addition reactions with aromatic or heteroaromatic aldehyde derivatives are powerful C-C bond-forming reactions that can provide chiral hydroxy compounds with stereogenic hydroxy functional groups. Therefore, the development of asymmetric nucleophilic addition is an ongoing challenge in organic synthesis. Following the first demonstration of the catalytic asymmetric nucleophilic addition with biomass-derived furfural by the Yamamoto group in 1997 [41], numerous reports with regard to catalytic asymmetric reactions of furfural have been published including the reaction of allylation [42], aldol reactions [43, 44], nitroaldol (henry) reaction [45, 46], alkylation [47, 48, 49], acylation [50], the Reformatsky reaction [51], the Nozaki-Hiyama reaction [52], alkynylation [53], and hydroboration [54] with various types of catalysts (Figure 24). However, the enantioselective catalytic nucleophilic addition reaction of 5-hydroxymethylfurfural (HMF) has not yet been reported.
5. Conclusion
As we have shown in this book chapter, a variety of synthetic approaches, such as cycloaddition reactions, Friedel-Crafts reactions, and nucleophilic addition reactions, are elegant methodologies that have been efficiently used for the enantioselective reaction of biomass-derived furans. While Friedel-Crafts and nucleophilic addition reactions serve various furan derivatives with a chiral carbon atom in the α-position, enantioselective cyclization reactions using furans as the 4π diene component affords chiral dihydrofuran or tetrahydrofuran derivatives. Synthesizing chiral synthons or highly functionalized products derived from furan may show great potential not only for the creation of new libraries that could lead to the development of biologically active compounds but also for stimulating further research toward versatile applications of these molecules via another asymmetric catalysis. There is no doubt that the further development of catalytic enantioselective reactions with biomass-derived furans will continue to provide exciting results in near future.
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