Inorganic chemistry, anintramolecular Diels-Alder cycloaddition is aDiels–Alder reaction in which thediene and thedienophile are both part of the samemolecule.[1] The reaction leads to the formation of thecyclohexene-like structure as usual for a Diels–Alder reaction, but as part of a more complex fused or bridged cyclic ring system. This reaction can gives rise to various natural derivatives ofdecalin.[2]
Because the two reacting groups are already attached, two basic modes of addition are possible in this reaction. Depending on whether the tether that links to the dienophile is attached to the end or the middle of the diene, fused or bridged polycyclic ring systems can be formed.[3]
The tether than attaches the two reacting groups also affects the geometry of the reaction. As a result of itsconformational and other structural restrictions, the exo vs endo results[4] are usually not based on the simple (intermolecular) Diels–Alder reaction effects.
An intramolecular Diels-Alder reaction was one of the steps in atotal synthesis ofgibberellic acid.[5][6] Colour-coding: diene is blue, dienophile is red
^Corey, E. J.; Danheiser, Rick L.; Chandrasekaran, Srinivasan; Keck, Gary E.; Gopalan, B.; Larsen, Samuel D.; Siret, Patrice; Gras, Jean Louis (1978). "Stereospecific total synthesis of gibberellic acid".Journal of the American Chemical Society.100 (25):8034–8036.Bibcode:1978JAChS.100.8034C.doi:10.1021/ja00493a056.
^A.C Burns; C.J Forsyth (2008). "Intramolecular Diels-Alder/Tsuji Allylation Assembly of the Functionalized trans-Decalin of Salvinorin A".Organic Letters.10 (1):97–100.doi:10.1021/ol7024058.PMID18062692.
^S. Chackalamannil; R.J Davies; Y. Wang; et al. (1999). "Total Synthesis of (+)- Himbacine and (+)-Himbeline".J. Org. Chem.64 (6):1932–1940.doi:10.1021/jo981983+.PMID11674285.
^B. Lygo; M. Bhatia; J.W.B Cooke; D.J Hirst (2003). "Synthesis of (+/-)- solanapyrones A and B".Tetrahedron Letters.44 (12): 2529.doi:10.1016/S0040-4039(03)00288-0.
