Introduction In 1950, the chemists Otto Paul Hermann Diels, from Germany, and Kurt Alder, originally born in Prussia and then moved to Germany after World War I, received the Nobel Prize in chemistry for the discovery of a new way to synthesize cyclic molecules. Aptly titled the Diels-Alder Cycloaddition Reaction, this new mechanism allowed conjugated dienes to undergo addition reactions with a...

A series of 10,13-disubstituted 16-membered macrolides was synthesized using nitroso Diels-Alder reactions of leucomycin A7. Despite the extensive constituent functionalities in leucomycin, the hetero cycloaddition reactions proceeded in a highly regio- and stereoselective fashion. Subsequent chemical modifications of the nitroso cycloadducts, including N-O bond reduction, were also conducted. ...

The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promis...

A new simple and efficient method for the synthesis of 2-phenylnaphthalenes from electron-rich 1-styryl-2-methoxybenzenes has been described. The reaction proceeds via TFA catalyzed C-C bond cleavage followed by intermolecular [4+2]-Diels-Alder cycloaddition of an in situ formed styrenyl trifluoroacetate intermediate. The quantum chemical calculations identified the transition state for the cyc...

A family of furoquinolines were efficiently obtained through a tandem acetalization/cycloisomerization process catalyzed by (5 mol%) silver imidazolate polymer and triphenylphosphine, and diversity was brought by the use of 7 different alcohol groups. From these furoquinolines, 3 examples of reduced derivatives could be obtained (d.r. up to 94 : 6), 10 different spiroketal derivatives by hetero...

diels–alder [2+4] cycloaddition products of the reaction between c20 and c4h4x2 or c2o2x2 (x = h, f, cl, ch3, nh2, no2, and oh) were studied atb3lyp level of theory with 6-31g, 6-31g(d, p) and 6-311g(d, p) basis sets. the homo–lumo gaps of kohn–sham orbitals for most of the adducts show evident increase compared with the gap value of c20, suggestive of more stability in the adducts. the thermod...

Pentacyclic analogues of the potent voltage-gated sodium ion channel agonist batrachotoxin can be accessed through an intermediate furan by exploiting Diels-Alder cycloaddition reactions with ring-strained dienophiles. The use of 3-bromofuran as a 1,2-dianion equivalent, the application of carbamate reductive N-alkylation for homomorpholine ring assembly, and the demonstration of CsF as an effe...

The enantioselective total syntheses of 11-acetoxy-4-deoxyasbestinin D and asbestinin-12 have been completed. A glycolate aldol reaction provided a diene useful for ring-closing metathesis to form an oxonene, which was ultimately employed as a template to execute a highly stereoselective intramolecular Diels-Alder cycloaddition, forming the hydroisobenzofuran moiety. The absolute configuration ...

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...

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...