Detailed kinetic analyses of inverse electron-demand Diels–Alder cycloaddition and nitrilimine-alkene/alkyne 1,3-diploar cycloaddition reactions were conducted and the reactions were applied for rapid protein bioconjugation. When reacted with a tetrazine or a diaryl nitrilimine, strained alkene/alkyne entities including norbornene, trans-cyclooctene, and cyclooctyne displayed rapid kinetics. To...

N-Cinnamoyl-9-aminoanthracenes cyclise with PPA or triflic acid to form novel 2-azahexacyclo[10.6.6.0(1,5).0(6,11).0(13,18).0(19,24)]tetracosa-6(11),7,9,13,15,17,19(24),20,22-nonaen-3-ones. In contrast, both N-cinnamoyl-N-methyl-9-(2-aminomethyl)anthracene and N-cinnamoyl-9-(2-aminoethyl)anthracene undergo an intramolecular Diels-Alder cycloaddition.

In these experiments, which were used in the problemsolving mode (1), the stereoselectivity of the Diels–Alder cycloaddition of N-phenylmaleimide to furan is deduced by the characteristic splitting patterns in the proton-NMR spectra. The relationship of coupling constants to dihedral angle, as described by the Karplus equation, is illustrated. The data can also be used to demonstrate the concep...

Dimeric forms of norbornadiene and benzonorbornadiene were synthesized starting with known monobromide derivatives. The Diels-Alder cycloaddition reaction of dimers with TCNE and PTAD was investigated and new norbornenoid polycyclics were obtained. All compounds were characterized properly using NMR spectroscopy.

Anti-Bredt alkenes, bicyclic molecules that contain a bridgehead double bond, were for many years regarded as chemical curiosities. The type 2 intramolecular Diels-Alder (IMDA) reaction provides a one-step entry into this fascinating class of molecules. The reaction has made available numerous anti-Bredt alkenes for structural and chemical studies. X-ray crystallography has revealed the magnitu...

Chemical redox reactions have been exploited to transform unreactive vinylferrocene into a powerful dienophile for the Diels-Alder reaction and reactive substrate for thiol addition reactions upon conversion to its ferrocenium state. We have further investigated the ability of these reactions to facilitate redox-auxiliary-like reactivity by further hydrogenolyisis of the Diels-Alder adduct to t...

Strongly electron-deficient dendralenes prepared in 3 steps from methyl propiolate undergo smooth diene-transmissive Diels–Alder reactions with strongly dienophiles.

A new synthesis of dibenzopyranones 14 is reported via the Diels-Alder cycloaddition of 4-cyanocoumarins 12 with 1-silyloxydienes 10 to give the adducts 13 which are then converted into 14 in one step via treatment with base and loss of the cyano and silyloxy groups.

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereosel...