Synthesis of 1,5-Enynes by Brønsted Acid Catalyzed Substitution of Propargylic Alcohols and One-Pot Synthesis of Bicyclo[3.1.0]hexenes

Roberto Sanz; Alberto Martínez; Delia Miguel; Julia M. Álvarez-Gutiérrez; Félix Rodríguez

doi:10.1055/s-2007-983831

PSP

Synthesis of 1,5-Enynes by Brønsted Acid Catalyzed Substitution of Propargylic Alcohols and One-Pot Synthesis of Bicyclo[3.1.0]hexenes

Roberto Sanz*^a, Alberto Martínez^a, Delia Miguel^a, Julia M. Álvarez-Gutiérrez^a, Félix Rodríguez*^b
^a Departamento de Química, Área de Química Orgánica, Facultad de Ciencias, Universidad de Burgos, Pza. Misael Bañuelos s/n, 09001-Burgos, Spain
Fax: +34(947)258831; e-Mail: rsd@ubu.es;
^b Instituto Universitario de Química Organometálica ‘Enrique Moles’, Universidad de Oviedo, C/ Julián Clavería 8, 33006-Oviedo, Spain
Fax: +34(98)5103447; e-Mail: frodriguez@uniovi.es;

Abstract

Alle Artikel dieser Rubrik

Abstract

A practical air and moisture tolerant procedure for the preparation of 1,5-enynes from propargylic alcohols by the Brønsted acid catalyzed direct propargylic substitution of the hydroxy group with allylsilanes is described. Also, a straightforward sequential catalytic protocol for the synthesis of bicyclo[3.1.0]hexane derivatives, from readily available starting materials, is presented.

Key words

catalysis - allylations - alcohols - enynes - tandem reactions

Volltext

Referenzen

References

1a Nicholas KM. Acc. Chem. Res. 1987, 20: 207

1b Teobald BJ. Tetrahedron 2002, 58: 4133

2 Nishibayashi Y. Inada Y. Hidai M. Uemura S. J. Am. Chem. Soc. 2003, 125: 6060

3 Luzung MR. Toste FD. J. Am. Chem. Soc. 2003, 125: 15760

4 Georgy M. Boucard V. Campagne J.-M. J. Am. Chem. Soc. 2005, 127: 14180

5 Zhan Z.-P. Yang W.-Z. Yang R.-F. Yu J.-L. Li J.-P. Liu H.-J. Chem. Commun. 2006, 3352

6 Kabalka GW. Yao M.-L. Borella S. J. Am. Chem. Soc. 2006, 128: 11320

7a Sanz R. Martínez A. Álvarez-Gutiérrez J.-M. Rodríguez F. Eur. J. Org. Chem. 2006, 1383

7b Sanz R. Martínez A. Miguel D. Álvarez-Gutiérrez J.-M. Rodríguez F. Org. Lett. 2007, 9: 727

8 Sanz R. Martínez A. Miguel D. Álvarez-Gutiérrez J.-M. Rodríguez F. Adv. Synth. Catal. 2006, 348: 1841

9 Zhang L. Sun J. Kozmin SA. Adv. Synth. Catal. 2006, 348: 2271

10a Mamane V. Gress T. Krause H. Fürstner A. J. Am. Chem. Soc. 2004, 126: 8654

10b Harrak Y. Blaszykowski C. Bernard M. Cariou K. Mainetti E. Mouries V. Dhimane AL. Fensterbank L. Malacria M. J. Am. Chem. Soc. 2004, 126: 8656

10c Luzung MR. Markham JP. Toste FD. J. Am. Chem. Soc. 2004, 126: 10858

10d Nishibayashi Y. Yoshikawa M. Inada Y. Hidai M. Uemura S. J. Am. Chem. Soc. 2004, 126: 16066

11 Concurrent tandem catalysis constitutes a significant challenge for synthetic chemists and presents a number of opportunities to improve chemical transformations, see: Wasilke J.-C. Obrey SJ. Baker RT. Bazan GC. Chem. Rev. 2005, 105: 1001

12 For the preparation of 2b, see: Hayashi T. Kabeta K. Hamachi I. Kumada M. Tetrahedron Lett. 1983, 24: 2865

13

In some cases, and when refluxing conditions are required, competitive formation of the corresponding symmetric ether is observed (ca. 20% isolated yield).

Some interesting processes in which different transition-metal catalysts work in the same medium have been reported. However, in most cases, the reaction conditions have to be changed. See, for instance:

14a Jeong N. Seo SD. Shin JY. J. Am. Chem. Soc. 2000, 122: 10220

14b Son SU. Park KH. Chung YK. J. Am. Chem. Soc. 2002, 124: 6838