A New One-Pot Synthetic Method for Selenium-Containing Medium-Sized α,β-Unsaturated Cyclic Ketones [¹]

Abstract

The reaction of tetrahydroselenopyran-2-one (7) with ethynyllithiums 20a-h, followed by treatment with aqueous 5% H₂SO₄ successfully led to a two-carbon ring expansion to give the 2-substituted 5,6,7,8-tetrahydroselenocin-4-ones 21a-h in 43-95% yields. Seven- to nine-membered γ-selena-α,β-unsaturated cyclic ketones 22-26 and a 5,6,7,8-tetrahydrotellurocin-4-one 27 were also prepared from the corresponding selenolactones or tellurolactone in a one-pot reaction.

selenolactone - ethynyllithium - ring expansion - selenium - selenoketone

References

1 This paper constitutes Part 26 in the ‘Studies on Tellurium-Containing Heterocycles’. For Part 25, see: Ohyanagi K. Sashida H. Heterocycles  2006,  68:  505 

2a Wirth T. Tetrahedron  1999,  55:  1 

2b Litvinov VP. Dyachenko VD. Russ. Chem. Rev.  1997,  66:  923 

2c Organoselenium Chemistry, In Topics in Current Chemistry   Vol. 208:  Wirth T. Springer; Berlin: 2000. 

2d Organoselenium Chemistry, A Practical Approach   Back TG. Oxford University Press; Oxford: 1999. 

3a Selenium in Biology and Medicine   Wengel A. Springer; Berlin: 1989. 

3b Burk RF. Selenium in Biology and Human Health   Springer; New York: 1994. 

3c Xu Y. Kool ET. J. Am. Chem. Soc.  2000,  122:  9040 

3d Koketsu M. Ishihara H. Curr. Org. Chem.  2003,  7:  175 

4 Hesse M. Ring Enlargement in Organic Chemistry   VCH; Weinheim: 1991. 

5 Sashida H. Kurahashi H. Tsuchiya T. J. Chem. Soc., Chem. Commun.  1991,  802 

6a Sashida H. Ito K. Tsuchiya T. J. Chem. Soc., Chem. Commun.  1993,  1493 

6b Sashida H. Ito K. Tsuchiya T. Chem. Pharm. Bull.  1995,  43:  19 

7a Sashida H. Heterocycles  1998,  48:  631 

7b Sashida H. Satoh H. Chem. Pharm. Bull.  2004,  52:  413 

8a Sashida H. Rev. Heteroatom Chem.  2000,  22:  59 

8b Sashida H. J. Synth. Org. Chem. Jpn.  2001,  59:  355 

9 Lemaire Ch. Luxen A. Christians L. Guillaume M. J. Heterocycl. Chem.  1983,  20:  811 

10a Sashida H. Ohyanagi K. Heterocycles  1999,  51:  17 

10b Sashida H. Ohyanagi K. Minoura M. Akiba K.-y. J. Chem. Soc., Perkin Trans. 1  2002,  606 

11 Blum A. Hess W. Studer A. Synthesis  2004,  226 

12 Sashida H. Synthesis  1998,  745 

13 Oikawa M. Oikawa H. Ichihara A. Tetrahedron  1995,  51:  6237 

14a Julia M. Melamed R. Gombert R. Ann. Inst. Pasteur  1965,  109:  343 ; Chem. Abstr. 1965, 63, 13191c

14b Marchant R. Wickeert JW. Marvel CS. J. Am. Chem. Soc.  1927,  49:  1828 

15 Fourneau E. Florence G. Bull. Soc. Chim.  1928,  43:  1027 ; Chem. Abstr. 1928, 22, 3227