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Imine Diels–Alder Reaction
The imine Diels–Alder reaction involves the transformation of all-carbon dienes and imine dienophiles into tetrahydropyridines. Introduction Imines may be employed as dienophiles in hetero-Diels-Alder reactions. These reactions involve the lowest unoccupied molecular orbital (LUMO) of the imine, meaning that imines substituted with electron-withdrawing groups on nitrogen are the most reactive. The reaction may be thermal, in refluxing solvents such as benzene or others typical for Diels–Alder reactions, or acid catalyzed, again using common Diels–Alder Lewis acids such as boron trifluoride or zinc chloride. It may proceed via a concerted, +2cycloaddition mechanism, although in cases of extreme polarization, addition to the imine followed by nitrogen nucleophilic attack (the "Mannich-Michael" pathway) occurs. Cyclic, acyclic, and tethered imines have all been employed in the reaction with success. Simple alkyl or aryl amines are often generated ''in situ'' by combining an ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Diels–Alder Reaction
In organic chemistry, the Diels–Alder reaction is a chemical reaction between a conjugated diene and a substituted alkene, commonly termed the dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted mechanism. More specifically, it is classified as a thermally-allowed +2cycloaddition with Woodward–Hoffmann symbol π4s_+_π2s.html" ;"title="sub>π4s + π2s">sub>π4s + π2s It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in the synthesis of natural products and new materials. The ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Aza-Diels–Alder Reaction
The aza-Diels–Alder reaction converts imines and dienes to tetrahydropyridines. This organic reaction is a modification of the Diels–Alder reaction. The nitrogen atom can be part of the diene or the dienophile. The imine is often generated in situ from an amine and formaldehyde. An example is the reaction of cyclopentadiene with benzylamine to an aza norbornene. In the enantioselective Diels–Alder (DA) reaction of an aniline, formaldehyde and a cyclohexenone catalysis, catalyzed by (S)-proline even the diene is masked. The catalytic cycle starts with the reactions of the aromatic amine with formaldehyde to the imine and the reaction of the ketone with proline to the diene. The second step, an endo trig cyclisation, is driven to one of the two possible enantiomers (99% enantiomeric excess, ee) because the imine nitrogen atom forms a hydrogen bond with the carboxylic acid group of proline on the Si face. Hydrolysis of the final complex releases the product and regenerat ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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