Practical and Robust Method for the Preparation of Seebach and Fráter’s Chiral Template, cis-2-Substituted 5-Methyl(or Phenyl)-1,3-dioxolan-4-ones

Ryohei Nagase; Yumiko Oguni; Tomonori Misaki; Yoo Tanabe

doi:10.1055/s-2006-950295

PSP

Practical and Robust Method for the Preparation of Seebach and Fráter’s Chiral Template, cis-2-Substituted 5-Methyl(or Phenyl)-1,3-dioxolan-4-ones

Ryohei Nagase, Yumiko Oguni, Tomonori Misaki, Yoo Tanabe*
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Japan
Fax: +81(79)5659077; e-Mail: tanabe@kwansei.ac.jp;

Abstract

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Abstract

A practical and highly stereoselective method for the preparation of three cis-2-substituted 5-methyl (or phenyl)-1,3-dioxolan-4-ones 3a and 7a (Seebach and Fráter’s chiral template), and a new modified analogue 7b has been developed. The present robust method utilized reactive 2-methoxy-1,3-dioxolane intermediate 4 and the reaction proceeded more smoothly under milder reaction conditions than in previously reported methods. Desired products 3a, 7a, and 7b were easily purified by distillation or recrystallization, i.e. column chromatographic purification, was not necessary.

Key words

(S)-lactic acid - (S)-mandelic acid - cyclocondensation - acid catalyst - 2,5-disubstituted-1,3-dioxolan-4-ones

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Referenzen

References

1a Seebach D. Naef R. Helv. Chim. Acta 1981, 64: 2704

1b Fráter G. Müller U. Günther W. Tetrahedron Lett. 1981, 22: 4221

1c Seebach D. Sting AR. Hoffmann M. Angew. Chem., Int. Ed. Engl. 1996, 35: 2708

1d Clayden J. Greeves N. Warren S. Wothers P. Organic Chemistry Oxford University Press; New York: 2001. p.855

2a Seebach D. Naef R. Calderari G. Tetrahedron 1984, 40: 1313

2b Greiner A. Ortholand J.-Y. Tetrahedron Lett. 1992, 33: 1897

2c Battaglia A. Barbaro G. Giorgianni P. Guerrini A. Bertucci C. Geremia S. Chem. Eur. J. 2000, 6: 3551

2d Grover PT. Bhongle NN. Wald SA. Senanayake CH. J. Org. Chem. 2000, 65: 6283

2e Dounay AB. Urbanek RA. Frydrychowski VA. Forsyth CJ. J. Org. Chem. 2001, 66: 938

3a Mase T. Houpis IN. Akao A. Dorziotis I. Emerson K. Hoang T. Iida T. Itoh T. Kamei K. Kato S. Kato Y. Kawasaki M. Lang F. Lee J. Lynch J. Maligres P. Molina A. Nemoto T. Okada S. Reamer R. Song JZ. Tschaen D. Wada T. Zewge D. Volante RP. Reider PJ. Tomimoto K. J. Org. Chem. 2001, 66: 6775

3b Blay G. Fernández I. Monje B. Pedro JR. Ruiz R. Tetrahedron Lett. 2002, 43: 8463

4a Heckmann B. Mioskowski C. Yu J. Falck JR. Tetrahedron Lett. 1992, 33: 5201

4b Heckmann B. Mioskowski C. Bhatt RK. Falck JR. Tetrahedron Lett. 1996, 37: 1421

4c Heckmann B. Mioshowski C. Lumin S. Falck JR. Wei S. Capdevila JH. Tetrahedron Lett. 1996, 37: 1425

5a Barbaro G. Battaglia A. Guerrini A. Bertucci C. Tetrahedron: Asymmetry 1997, 8: 2527

5b Barbaro G. Battaglia A. Guerrini A. J. Org. Chem. 1999, 64: 4643

6

In our hands, comparable experiments using pentane and heptane (bp 98 °C) as solvents revealed that they have a significant effect on the stereoselectivity; cis/trans = 97:3 (pentane) and 54:46 (heptane). The direct method largely depends on the reaction temperature of azeotropic boiling points.

7 Misaki T. Ureshino S. Nagase R. Oguni Y. Tanabe Y. Org. Process Res. Dev. 2006, 10: 500

8 Related method using crystalline dioxolane in diastereomerically pure form was reported: Ortholand J.-Y. Vicart N. Greiner A. J. Org. Chem. 1995, 60: 1880