In organic chemistry, an intramolecular Diels-Alder cycloaddition is a
DielsâAlder reaction in which the
diene and the
dienophile are both part of the same molecule.[1] The reaction leads to the formation of the
cyclohexene-like structure as usual for a DielsâAlder reaction, but as part of a more complex fused or bridged cyclic ring system. This reaction can gives rise to various natural derivatives of
decalin.[2]
Reaction products
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 its
conformational and other structural restrictions, the exo vs endo results[4] are usually not based on the simple (intermolecular) DielsâAlder reaction effects.
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ISBN0716772663.
^P.Y Bruice (2007). Organic Chemistry. Pearson Education, Inc.
^Corey, E. J.;
Danheiser, Rick L.; Chandrasekaran, Srinivasan; Siret, Patrice; Keck, Gary E.; Gras, Jean Louis (1978). "Stereospecific total synthesis of gibberellic acid. A key tricyclic intermediate". Journal of the American Chemical Society. 100 (25): 8031â8034.
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10.1021/ja00493a055.
^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): 8034â8036.
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): 97â100.
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): 1932â1940.
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.