Double Mitsunobu Reactions of cis-Cycloalk-2-ene-1,4-diols and 3,4-Epoxycycloalkenes: Rearrangements of Allylic Diazides

Süleyman Göksu; Cagri Ozalp; Hasan Seçen; Yaşar Sütbeyaz; Emin Saripinar

doi:10.1055/s-2004-831258

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Double Mitsunobu Reactions of cis-Cycloalk-2-ene-1,4-diols and 3,4-Epoxycycloalkenes: Rearrangements of Allylic Diazides

Süleyman Göksu^a, Cagri Ozalp^a, Hasan Seçen*^a, Yaşar Sütbeyaz*^a, Emin Saripinar^b
^a Department of Chemistry, Faculty of Arts and Sciences, Ataturk University, 25240 Erzurum, Turkey
Fax: 90(442)2360948; e-Mail: hsecen@atauni.edu.tr;
^b Department of Chemistry, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey

Abstract

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Abstract

Double Mitsunobu reactions of cis-cycloalk-2-ene-1,4-diols and 3,4-epoxycloalkenes were investigated. cis-3,5-Diazidocyclopentene, cis-3,4-diazidocyclooctene, and cis-3,8-diazidocyclooctene were formed as sole products via the Mitsunobu reaction. cis-Cyclohex-2-ene-1,4-diol, 3,4-epoxycyclohexene and trans-2-azidocyclohex-3-en-1-ol gave a mixture of cis-3,6-diazidocyclohexene and cis-3,4-diazidocyclohexene via a sigmatropic rearrangement. In the same manner, cis-cyclohept-2-ene-1,4-diol, 3,4-epoxycycloheptene and trans-2-azidocyclohept-3-en-1-ol gave a mixture of cis-3,7-diazidocycloheptene and cis-3,4-diazidocycloheptene. Experimental results were explained by theoretical PM3 calculations.

Key Words

allylic diazides - Mitsunobu reaction - sigmatropic rearrangement

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Referenzen

References

1 For an excellent review, see: Scriven EFV. Turnbull K. Chem. Rev. 1988, 88: 297

2 Skarzewski J. Gupta A. Tetrahedron: Asymmetry 1997, 8: 1861

3 Göksu S. Seçen H. Sütbeyaz Y. Synthesis 2002, 2373

4a

The Mitsunobu reaction may proceed with an S_N1 mechanism in some unsaturated systems

4b Review: Mitsunobu O. Synthesis 1981, 1

4c Review: Hughes DL. Org. React. 1992, 42: 335

Rearrangement of allylic azides is reported, see:

5a Gagneux A. Winstein S. Young WG. J. Am. Chem. Soc. 1960, 82: 5956

5b Van der Werf CA. Heasley VL. J. Org. Chem. 1966, 31: 3534

5c Arimoto M. Yamaguchi H. Fujita E. Ochiai M. Nagao Y. Tetrahedron Lett. 1987, 28: 6289

5d Murahashi S. Taniguchi Y. Imada Y. Tanigawa Y. J. Org. Chem. 1989, 54: 3292

5e Trost BM. Pulley SR. Tetrahedron Lett. 1995, 36: 8737

5f Trost BM. Cook GR. Tetrahedron Lett. 1996, 37: 7485

6 Pearson AJ. Lai YS. Lu W. Pinkerton AA. J. Org. Chem. 1989, 54: 3882

7 Kaneko C. Sugimoto A. Tanaka S. Synthesis 1974, 876

8 Seçen H. Gültekin MS. Sütbeyaz Y. Balci M. Turk. J. Chem. 1993, 17: 108 ; Chem. Abstr. 1994, 120, 271002

9 Suzuki M. Oda Y. Hamanaka N. Noyori R. Heterocycles 1990, 30: 517

10 Horinaka A. Nakashima R. Yoshikawa M. Matsuura T. Bull. Chem. Soc. Jpn. 1975, 48: 2095

11 Crandall JK. Banks DB. Colyer RA. Watkins RJ. Arrington JP. J. Org. Chem. 1968, 33: 423

12a Yano T. Kobayashi H. Ueno K. Bull. Chem. Soc. Jpn. 1973, 46: 985

12b Mete E. Maras A. Secen H. Russ. Chem. Bull. 2003, 52: 1879

13 Hoenig H. Seufer-Wasserthal P. Fulop F. J. Chem. Soc., Perkin Trans. 1 1989, 2341

14 Sasaki T. Kanematsu K. Yukimoto Y. J. Chem. Soc., Perkin Trans. 1 1973, 375

15 The first and stereospecific preparation of cis-3,4-diazidocyclooctene (17) from cycloocta-1,3-diene via iodunium azide and sodium azide displacement has been reported: Sasaki T. Kanematsu K. Yukimoto Y. J. Org. Chem. 1972, 37: 890