Synthesis of (+,-) 3,4-disubstituted 3,4-dihydro-2H-thiopyrans via a diastereoselective hetero Diels-Alder reaction

Tetrahedron Letters

Volumn 38, Issue 6, 1997, Pages 1033-1036

  Marchand, Anne ^a   Pradère, Jean Paul ^a   Guingant, André ^a  

^a Centre National de la Recherche Scientifique   (France)

Author keywords

[No Author keywords available]

Indexed keywords

THIOPYRAN DERIVATIVE;

ARTICLE; CHIRALITY; DIASTEREOISOMER; DRUG SYNTHESIS; IN VITRO STUDY; INFRARED SPECTROPHOTOMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0031562048     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(96)02495-1     Document Type: Article

References (19)

1. 1 Pradère, J.P.; Tonnard, F.; Abouelfida, A.; Cellerin, C.; Andriamanamibaja, M.; Jousseaume, B.; Toupet, L.; Guénot, P. Bull Soc. Chim. Fr., 1993, 130, 610-619 and references cited therein.
2. 2 Marchand, A.; Mauger, D.; Guingant, A.; Pradère, J.P. Tetrahedron: Asymmetry, 1995, 6, 853-856.
3. 3 Cellerin, C.; Tea, G.C; Pradère, J.P.; Guingant, A.; Guénot, P. Sulfur Lett. 1988, 8, 205-209.
4. 4 For recent examples of exo-selective Diels-Alder cycloadditions featuring 2-azadienes, see Morel, G.; Marchand, E.; Pradère, J.P.; Toupet, L.; Sinbandhit, S. Tetrahedron, 1996, 52, 10095-10112 and references cited therein.
5. 5 Bignebat, J; Quiniou, H.; Lozac'h, N. Bull. Soc. Chim. Fr. 1969, 127-135
6. 6 Early studies concerning the cycloaddition reaction of 4-dimethylamino-2-aryl-1-thiabutadiene to a variety of dienophiles in benzene solution at reflux, concluded to the exclusive formation of exo adducts. Pradère, J.P.; N'Guessan, T.; Quiniou, H.; Tonnard, F. Tetrahedron, 1975, 31, 3059-3064.
7. 7 At the PM3 level the calculated HOMO energies for dienes 1 and 4 are -9.05ev and -8.50ev , respectively.
8. 8 Semi-empirical calculations (PM3 hamiltonian) have been carried out on the heat of formation of adducts endo 6a, 6b and exo 7a,7b. The computational results show that exo adducts 7a and 7b are more stable than endo adducts 6a and 6b by 6.36 and 13.68 kJ/mol, respectively.
9. 3, δ): 29.9, 40.3, 41.2, 43.1, 62.1, 62.2, 117.8, 126.7, 128.6, 131.9, 137.2, 139.5, 153.5, 174.5.
10. 10 At the PM3 level "endo 1" conformation is more stable than "endo 2" conformation by 12.60 kJ/mol for 7a .
11. 11 Toupet, L. Université de Rennes. Details of the crystal structure of 6a will be reported in a forthcoming full paper.
12. 12 For some recent examples of hetero Diels-Alder reactions involving dienes bearing some structural similarities with diene 4, see: a) Motoki, S.; Saito, T.; Karakasa, T.; Kato, H.; Matsushita, T.; Hayashibe, S. J.Chem.Soc., Perkin Trans. 1, 1991, 2281-2283.
13. b) Saito, T.; Karakasa, T.; Fuji, H.; Furuno, E.; Suda, H.; Kobayashi, K. J.Chem.Soc., Perkin Trans. 1, 1994, 1359-1362.
14. c) Saito, T.; Fujii, H.; Hayashibe, S.; Matsushita, T.; Kato, H.; Kobayashi, K. J.Chem.Soc., Perkin Trans, 1, 1996, 1897-1903.
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19. h) Bell, A.S.; Fishwick, C.W.G.; Reed, J. Tetrahedron Lett., 1996, 37, 123-126.