Tandem Ene-Reaction/Intramolecular Sakurai Cyclisation (IMSC): A Novel Access to Polysubstituted Tetrahydropyrans and γ-Butyrolactones Using a Unique Allylation Strategy

István E. Markó; Raphaël Dumeunier; Cédric Leclercq; Bernard Leroy; Jean-Marc Plancher; Abdelaziz Mekhalfia; Daniel J. Bayston

doi:10.1055/s-2002-28506

SPECIALTOPIC

Tandem Ene-Reaction/Intramolecular Sakurai Cyclisation (IMSC): A Novel Access to Polysubstituted Tetrahydropyrans and γ-Butyrolactones Using a Unique Allylation Strategy

István E. Markó*, Raphaël Dumeunier, Cédric Leclercq, Bernard Leroy, Jean-Marc Plancher, Abdelaziz Mekhalfia, Daniel J. Bayston
Université catholique de Louvain, Département de Chimie, Unité de Chimie Organique et Médicinale, Bâtiment Lavoisier, Place Louis Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Fax: +32(10)478033; e-Mail: marko@chim.ucl.ac.be;

Abstract

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Abstract

The ene-reaction between a variety of aldehydes and allylsilane 22 generates highly functionalised homoallylic alcohols 23. These adducts undergo a subsequent Intramolecular Sakurai Cyclisation (IMSC), affording in good yields polysubstituted tetrahydropyran derivatives. Furthermore, oxidative desilylation of 23 provides an efficient, connective access to a range of γ-butyrolactones and α-methylene-γ-butyrolactones.

Key words

ene-reactions - tetrahydropyrans - allylations - γ-butyrolactones - α-methylene-γ-butyrolactones

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References

For excellent reviews, see:

1a Perron F. Albizati KM. Chem. Rev. 1989, 89: 1617

1b Boivin TLB. Tetrahedron 1987, 43: 3309

1c Hoffmann HMR. Rabe J. Angew. Chem., Int. Ed. Engl. 1985, 24: 94

1d Petragnani N. Ferraz HMC. Silva GVJ. Synthesis 1986, 157

1e Elliott MC. J. Chem. Soc., Perkin Trans. 1 1998, 4175

1f Elliott MC. J. Chem. Soc., Perkin Trans. 1 2000, 1291

2a Y.-Yamashita M. Haddock RL. Yasumoto T. J. Am. Chem. Soc. 1993, 115: 1147

2b For the total synthesis of polycavernoside A, see: Fujiwara K. Murai A. Y.-Yamashita M. Yasumoto T. J. Am. Chem. Soc. 1998, 120: 10770

2c Paquette LA. Barriault L. Pissarnitski D. J. Am. Chem. Soc. 1999, 121: 4542

3a Leroy B. Dumeunier R. Markó IE. Tetrahedron Lett. 2000, 41: 10215

3b Dumeunier R. Markó IE. Tetrahedron Lett. 2000, 41: 10219

4 Mekhalfia A. Markó IE. Tetrahedron Lett. 1991, 32: 4779

5a For an excellent review, see: Langkopf E. Schinzer D. Chem. Rev. 1995, 95: 1375

5b See also: Markó IE. Chellé F. Tetrahedron Lett. 1997, 38: 2895

5c Yadav JS. Subba Reddy BV. Mahesh Kumar G. Murthy CVSR. Tetrahedron Lett. 2001, 42: 89 ; and references cited therein

6a Mekhalfia A. Markó IE. Adams H. Tetrahedron Lett. 1991, 32: 4783

6b Markó IE. Mekhalfia A. Tetrahedron Lett. 1992, 33: 1799

6c Markó IE. Mekhalfia A. Bayston DJ. Adams H. J. Org. Chem. 1992, 57: 2211

6d Markó IE. Bayston DJ. Mekhalfia A. Adams H. Bull. Soc. Chim. Belg. 1993, 102: 655

6e For a selected number of other beautiful applications, see: Mohr P. Tetrahedron Lett. 1993, 34: 6251

6f Mohr P. Tetrahedron Lett. 1995, 36: 2453

6g Suginome M. Iwanami T. Ito Y. J. Org. Chem. 1998, 63: 6096

6h Semeyn C. Blaauw RH. Hiemstra H. Speckamp WN. J. Org. Chem. 1997, 62: 3426

7a Markó IE. Bayston DJ. Tetrahedron Lett. 1993, 34: 6595

7b Markó IE. Plancher J.-M. Tetrahedron Lett. 1999, 40: 5259

8a Hosomi A. Sakurai H. Tetrahedron Lett. 1976, 1295

8b Chan TH. Fleming I. Synthesis 1979, 761

8c Fleming I. Dunogues J. Smithers R. Org. React. 1989, 37: 57

9 Gemal AL. Luche J.-L. J. Am. Chem. Soc. 1981, 103: 5454

10 Trost BM. Chan DMT. Nanninga TN. Org. Synth. 1984, 62: 58

11a Mikami K. Shimizu M. Chem. Rev. 1992, 92: 1021

11b Snider BB. In The Prins and Carbonyl Ene Reactions Vol. 2: Trost BM. Fleming I. Comprehensive Organic Synthesis, Pergamon; London: 1991. p.527

11c Snider BB. Rodini DJ. Kirk TC. Cordova R. J. Am. Chem. Soc. 1982, 104: 555

12a Castaneda A. Kucera DJ. Overman LE. J. Org. Chem. 1989, 54: 5695 ; and references cited therein

12b Perst H. Oxonium Ions in Organic Chemistry Verlag-Chemie; Weinheim: 1971.

12c Cloninger MJ. Overman LE. J. Am. Chem. Soc. 1999, 121: 1092

12d Coppi L. Ricci A. Taddei M. Tetrahedron Lett. 1987, 28: 973

12e Wei ZY. Wang D. Li JS. Chan TH. J. Org. Chem. 1989, 54: 5768

13a Yamamoto Y. Asao N. Chem. Rev. 1993, 93: 2207

13b Fleming I. In Allylsilanes, Allylstannanes and Related Systems Vol. 2: Trost BM. Fleming I. Comprehensive Organic Synthesis, Pergamon; London: 1991. p.563

14 Maruoka K. Itoh T. Sakurai M. Nonoshita K. Yamamoto H. J. Am. Chem. Soc. 1988, 110: 3588

15 Mikami K. Matsukawa S. Tetrahedron Lett. 1994, 35: 3133

16 Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis 1994, 639

17a To the best of our knowledge, only a single article is explicitly devoted to the synthesis and reactions of β-(trimethylsilylmethyl)ketones and lactones: Fleming I. Goldhill J. J. Chem. Soc., Perkin Trans. 1 1980, 1493

17b Three other limited examples of such compounds also appeared in: Paterson I. Tetrahedron 1988, 44: 4207

17c Bertrand M. Dulcere J.-P. Gil G. Tetrahedron Lett. 1980, 21: 1945

17d Bachi MD. Bosch E. Tetrahedron Lett. 1988, 29: 2581

18 Leroy B. Dumeunier R. Markó IE. Tetrahedron Lett. 2000, 41: 10215

19 Dumeunier R. Leclercq C. Markó IE. Tetrahedron Lett. 2002, 43: 2307

20 Corey EJ. Gilman NW. Ganem BE. J. Am. Chem. Soc. 1968, 90: 5616