Relative Migratory Aptitude of Substituents and Stereochemistry of Dyotropic Ring Enlargements of β-Lactones

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 13-14, 1997, Pages 1476-1478

  Mulzer, Johann ^a   Hoyer, Karsten ^b   Müller Fahrnow, Anke ^c  

^a Inst fur Org Chem der Univ   (Austria)

^b GOETHE UNIVERSITY   (Germany)

^c BAYER PHARMA AG   (Germany)

Author keywords

Dyotropy; Lactones; Reaction mechanisms; Rearrangements

Indexed keywords

EID: 0030841494     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199714761     Document Type: Article

References (20)

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2. M. T. Reetz, Angew. Chem. 1972, 84, 161-162; Angew. Chem. Int. Ed. Engl. 1972, 11, 129-130; ibid 1979, 91, 185-192 and 1979, 18, 173-180; Adv. Organomet. Chem. 1977, 16, 33; Tetrahedron 1973, 29, 2189-2194.
3. M. T. Reetz, Angew. Chem. 1972, 84, 161-162; Angew. Chem. Int. Ed. Engl. 1972, 11, 129-130; ibid 1979, 91, 185-192 and 1979, 18, 173-180; Adv. Organomet. Chem. 1977, 16, 33; Tetrahedron 1973, 29, 2189-2194.
4. M. T. Reetz, Angew. Chem. 1972, 84, 161-162; Angew. Chem. Int. Ed. Engl. 1972, 11, 129-130; ibid 1979, 91, 185-192 and 1979, 18, 173-180; Adv. Organomet. Chem. 1977, 16, 33; Tetrahedron 1973, 29, 2189-2194.
5. M. T. Reetz, Angew. Chem. 1972, 84, 161-162; Angew. Chem. Int. Ed. Engl. 1972, 11, 129-130; ibid 1979, 91, 185-192 and 1979, 18, 173-180; Adv. Organomet. Chem. 1977, 16, 33; Tetrahedron 1973, 29, 2189-2194.
6. M. T. Reetz, Angew. Chem. 1972, 84, 161-162; Angew. Chem. Int. Ed. Engl. 1972, 11, 129-130; ibid 1979, 91, 185-192 and 1979, 18, 173-180; Adv. Organomet. Chem. 1977, 16, 33; Tetrahedron 1973, 29, 2189-2194.
7. J. Mulzer, G. Brüntrup, Angew. Chem. 1979, 91, 840-841; Angew. Chem. Int. Ed. Engl. 1979, 18, 793-794.
8. J. Mulzer, G. Brüntrup, Angew. Chem. 1979, 91, 840-841; Angew. Chem. Int. Ed. Engl. 1979, 18, 793-794.
9. Review: D. J. Coveney in Comprehensive Organic Synthesis (Eds.: B. M. Trost, I. Fleming), Vol. 3 (Ed.: G. Pattenden), Pergamon Press, Oxford, 1991, p. 777.
10. T. H. Black, J. A. Fields, Synth. Commun. 1988, 18, 125-130.
11. T. H. Black, S. H. Eisenbeis, T. S. McDermott, S. L. Maluleka, Tetrahedron 1990, 46, 2307-2316.
12. The synthesis of the β-Mactones proceeded by carboxy-group activation with phenylsulfonyl chloride as described [9-10]. The diaslereomeric β- and γ-lactones were separated by HPLC under normal-phase conditions with a Nucleosil (5-7 μm) stationary phase and n-hexane/ethyl-acetate as eluent.
13. 2 in diethyl ether with ice cooling and stirring. After 12-60 h at 25-30°C the reactions were quenched with water, and the diastereomeric γ-lactones isolated from the ether phase [2]. Cross-check experiments showed that γ-lactones 3a-e remained unchanged under the reaction conditions.
14. M. T Reetz, A. Schmitz, X. Holdgrün, Tetrahedron Lett. 1989, 30, 5421-5424.
15. J. Mulzer, A. Pointner, A. Chucholowski, G. Brüntrup, J. Chem. Soc. Chem. Comm. 1979, 52-54.
16. W. Adam, J. Baeza, J.-C. Liu, J. Am. Chem. Soc. 1972, 94, 2000-2006.
17. -3 [14].
18. E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1996, p. 647-655.
19. The relative configuration of 2f was determined by hydrogenolysis to 4, which was characterized by X-ray crystallography [14].
20. Crystallographic data (excluding structure factors) for 1f and 4 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-179178. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: int. code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).