Diels–Alder Reaction
Introduction
The Diels-Alder reaction is a reaction that forms an unsaturated six membered ring between conjugated dienes and olefins (amphiphilic). Abbreviated as D-A reaction, also known as diene synthesis. This reaction is also called cycloaddition reaction because it involves the formation of cyclic products through cyclic transition state. Diels-Alder reaction is an electric ring reaction involving the [4+2] cycloaddition of 4π-electrons of conjugated dienes and 2π-electrons of dienophiles (alkenes or alkynes). This reaction involves the formation of new σ bonds is more stable in energy than π bonds. This reaction is of great significance in organic chemical synthesis, which was discovered by two German chemists Otto Paul Hermann Diels and his student Kurt Alder in 1928. They were awarded the Nobel Prize in Chemistry in 1950. 1
Application
The Diels-Alder reaction can be applied to the following synthesis:
The new Diels-Alder reaction between arynes and functionalized acyclic dienes can be used to synthesize widely used cis-substituted dihydronaphthalene building blocks.2
Synthesis of natural and unnatural polycarbonate and polyheterocyclic compounds through Diels Alder reaction.3
Based on the Diels-Alder reaction, substituted (tetrahydro) quinolines and various N-polyheterocyclic compounds can be constructed, including some alkaloids containing pyrroloquinoline or cyclopentaquinoline ring systems.4
The Imine Diels-Alder reaction (IDA), catalyzed by anhydrous indium trichloride (InCl3), yields pyrano [3,2-c] quinoline and indeno [2,1-c] quinolones. 5
The Double hetero Diels–Alder reactions can synthesize symmetrically substituted 1,8-diaza-9,10-anthraquinone derivatives with excellent yields.6
An oxazaborolidine derived from N-tosyl (αS,βR)-β-methyltryptophan can serve as a catalyst for the enantioselective Diels-Alder reaction of 2-bromoprolein and furan, resulting in the efficient synthesis of a series of chiral 7-oxabicyclo[2.2.1] heptene derivatives.7
Efficient and high-yield synthesis of brominated, boronated, and tin functionalized 1,2-Bis (trimethylsilyl) benzenes through the Diels Alder reaction. 1,2-Bis(trimethylsilyl)benzenes are key starting material for the synthesis of phenylacetylene precursors, Lewis acid catalysts, and some luminescent materials.8
Under ultrasonic treatment, Diels-Alder cycloaddition provides functionalized oxadiacycloolefins with high yield.9
Research Trends
Study the intramolecular and intermolecular Diels Alder reactions (Povarov reactions) of N-arylimines and various electron rich olefins.4
Ultrasonic irradiation promoted the Diels-Alder reaction of substituted furans with active dienophilic hydrocarbons such as dimethyl acetylenedicarboxylate (DMAD) and dimethyl maleate, and functionalized oxabicycloolefins were prepared with good yields.9
Based on Diels-Alder reaction of graphite and tetracyanoethylene, graphene adduct were efficiently synthesized by mechanical stripping of graphite.10
Cross linked hydrogels were prepared in aqueous medium by Diels Alder "click" reaction without catalyst.11
Asymmetric Diels-Alder reaction between N-acryloxyazolidinone and cyclopentadiene catalyzed by heterogeneous copper (II) bis (oxazoline) based polymer immobilized ion liquid phase (PIILP) system.12
Chiral oxazoborane-aluminum bromide complex is a highly efficient potential catalyst for enantioselective Diels-Alder reaction.13
Studies on Halocycloketenes as Strong Dieophiles in Intermolecular and Intramolecular Diels Alde cycloaddition.14
The application of chemical thermodynamics in the Diels Alder reaction of C60 fullerene with a series of anthracene (anthracene, 9,10-dimethylanthracene, tetraene and pentacene).15
References
1.Fringuelli F, Taticchi A. 2001. The Diels-Alder Reaction. https://doi.org/10.1002/0470845813
2.Dockendorff C, Sahli S, Olsen M, Milhau L, Lautens M. 2005. Synthesis of Dihydronaphthalenes via Aryne Diels?Alder Reactions: Scope and Diastereoselectivity. J. Am. Chem. Soc.. 127(43):15028-15029. https://doi.org/10.1021/ja055498p
3.Smith MB. 2011. Organic Synthesis.
4.Kouznetsov VV. 2009. Recent synthetic developments in a powerful imino Diels?Alder reaction (Povarov reaction): application to the synthesis of N-polyheterocycles and related alkaloids. Tetrahedron. 65(14):2721-2750. https://doi.org/10.1016/j.tet.2008.12.059
5.Babu G, Perumal PT. 1998. Convenient synthesis of pyrano[3,2-c]quinolines and indeno[2,1-c] quinolines by imino Diels-Alder reactions. Tetrahedron Letters. 39(20):3225-3228. https://doi.org/10.1016/s0040-4039(98)00397-9
6.Pérez JM, López-Alvarado P, Avendaño C, Menéndez J. 2000. Hetero Diels?Alder Reactions of 1-Acetylamino- and 1-Dimethylamino-1-azadienes with Benzoquinones. Tetrahedron. 56(11):1561-1567. https://doi.org/10.1016/s0040-4020(00)00058-2
7.Corey E, Loh T. 1993. Catalytic enantioselective diels-alder addition to furan provides a direct synthetic route to many chiral natural products. Tetrahedron Letters. 34(25):3979-3982. https://doi.org/10.1016/s0040-4039(00)60594-4
8.Reus C, Liu N, Bolte M, Lerner H, Wagner M. 2012. Synthesis of Bromo-, Boryl-, and Stannyl-Functionalized 1,2-Bis(trimethylsilyl)benzenes via Diels?Alder or C?H Activation Reactions. J. Org. Chem.. 77(7):3518-3523. https://doi.org/10.1021/jo3002936
9.Wei K, Gao H, Li WZ. 2004. Facile Synthesis of Oxabicyclic Alkenes by Ultrasonication-Promoted Diels?Alder Cycloaddition of Furano Dienes. J. Org. Chem.. 69(17):5763-5765. https://doi.org/10.1021/jo049210a
10.Ji Z, Chen J, Huang L, Shi G. High-yield production of highly conductive graphene via reversible covalent chemistry. Chem. Commun.. 51(14):2806-2809. https://doi.org/10.1039/c4cc09144b
11.García-Astrain C, Algar I, Gandini A, Eceiza A, Corcuera MÁ, Gabilondo N. 2015. Hydrogel synthesis by aqueous Diels-Alder reaction between furan modified methacrylate and polyetheramine-based bismaleimides. J. Polym. Sci. Part A: Polym. Chem.. 53(5):699-708. https://doi.org/10.1002/pola.27495
12.Doherty S, Knight JG, Ellison JR, Goodrich P, Hall L, Hardacre C, Muldoon MJ, Park S, Ribeiro A, de Castro CAN, et al. An efficient Cu(ii)-bis(oxazoline)-based polymer immobilised ionic liquid phase catalyst for asymmetric carbon?carbon bond formation. Green Chem.. 16(3):1470-1479. https://doi.org/10.1039/c3gc41378k
13.Liu D, Canales E, Corey EJ. 2007. Chiral Oxazaborolidine?Aluminum Bromide Complexes Are Unusually Powerful and Effective Catalysts for Enantioselective Diels?Alder Reactions. J. Am. Chem. Soc.. 129(6):1498-1499. https://doi.org/10.1021/ja068637r
14.Ross AG, Townsend SD, Danishefsky SJ. 2013. Halocycloalkenones as Diels?Alder Dienophiles. Applications to Generating Useful Structural Patterns. J. Org. Chem.. 78(1):204-210. https://doi.org/10.1021/jo302230m
15.Cataldo F, García-Hernández DA, Manchado A. 2015. Chemical Thermodynamics Applied to the Diels?Alder Reaction of C60Fullerene with Polyacenes. Fullerenes, Nanotubes and Carbon Nanostructures. 23(9):760-768. https://doi.org/10.1080/1536383x.2014.997354