Sequential Reaction of Glyoxal Hydrates with α-Bromo Ketones: Synthesis of 2,4,5-Triacyl-1,3-dioxolanes

Abstract

The sequential reaction between α-bromo ketones and glyoxal hydrates leads to 2,4,5-triacyl-1,3-dioxolanes. The reactions are promoted by a combination of triethylamine and lithium bromide, and a plausible mechanism is proposed. The reaction presumably proceeds via the condensation of glyoxal hydrates, the Williamson reaction and a cyclization sequentially. The reaction conditions are mild and operationally simple. Although the yields of the reactions are moderate, the products are formed stereoselectively.

Key words

glyoxal hydrate - enols - 1,3-dioxolanes - sequential reactions

References

• 1a Pellissier H. Tetrahedron  2006,  62:  2143 
• 1b Tietze LF. Chem. Rev.  1996,  96:  115 
• 1c Parsons PJ. Penkett CS. Shell AJ. Chem. Rev.  1996,  96:  195 
• 1d Winkler JD. Chem. Rev.  1996,  96:  167 
• 2a Lee W.-D. Kim K. Sulikowski GA. Org. Lett.  2005,  7:  1687 
• 2b Hodgson DM. Bailey JM. Barber CV. Drew MGB. Harrison T. J. Chem. Soc., Perkin Trans. 1  2000,  3432 
• 2c Smith AB. Condon SM. McCauley JA. Leazer JL. Leahy JW. Maleczka RE. J. Am. Chem. Soc.  1997,  119:  947 
• 2d Baxter EW. Reitz AB. J. Org. Chem.  1994,  59:  3175 
• 2e Crawford TC. Crawford SA. Adv. Carbohydr. Chem. Biochem.  1980,  37:  79 
• 3a Colobert F. Obringer M. Solladié G. Eur. J. Org. Chem.  2006,  1455 
• 3b Babudri F. Fiandanese V. Marchese G. Punzi A. J. Organomet. Chem.  2004,  689:  326 
• 3c McNulty J. Grunner V. Mao J. Tetrahedron Lett.  2001,  42:  5609 
• 4 Williams DBG. Caddy J. Blann K. Carbohydr. Res.  2005,  340:  1301 
• 5a Fuson RD. Mcburney CH. Holland WE. J. Am. Chem. Soc.  1937,  61:  3246 
• 5b Clerici A. Porta O. J. Org. Chem.  1989,  54:  3872 
• 7a Hurd CD. J. Chem. Educ.  1966,  43:  527 
• 7b Becker HD. Russell GA. J. Org. Chem.  1963,  28:  1895 
• 9a Blanchette MA. Choy W. Davis JT. Essenfeld AP. Masamune S. Roush WR. Sakai T. Tetrahedron Lett.  1984,  25:  2183 
• 9b Rathke MW. Nowak M. J. Org. Chem.  1985,  50:  2624 
• 10 Tsuge O. Kanemasa S. Yoshioka M. J. Org. Chem.  1988,  53:  1384 
• 11 Mattsson S. Dahlstrom M. Karlsson S. Tetrahedron Lett.  2007,  48:  2497 
• 12 Joshi KC. Pathak VN. Goyal MK. J. Heterocycl. Chem.  1981,  18:  1651 
• 13 Kornblum N. Powers JW. Anderson GJ. Jones WJ. Larson HO. Levand O. Weaver WM. J. Am. Chem. Soc.  1957,  79:  6562 
• 14 de Meester JWG. van der Plas HC. Middelhoven WJ. J. Heterocycl. Chem.  1987,  24:  441 
• 15 Moffett RB. Tiffany BD. Aspergren BD. Heinzelman RV. J. Am. Chem. Soc.  1948,  79:  1687 
• 16 Shao Q. Shi W. Zhang D. Li C. Acta Crystallogr., Sect. E  2006,  62:  o584 
• 17 Rosowsky A. Chen KKN. J. Org. Chem.  1973,  38:  2073 
• 18 Bedford CD. Miura M. Bottaro JC. Howd RA. Nolen HW. J. Med. Chem.  1986,  29:  1689 
• 19 Goslinski T. Golankiewicz B. De Clercq E. Balzarini J. J. Med. Chem.  2002,  45:  5052 
• 20 Chithralekha SK. Rajasekharan KN. Synth. Commun.  2002,  32:  1523 
• 21 Grundke G. Keese W. Rimpler M. Chem. Ber.  1985,  118:  4288 
• 22 Dubief R. Robbe Y. Fernandez JP. Subra G. Terol A. Eur. J. Med. Chem. Chim. Ther.  1986,  21:  461 

6

Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 686958 (4c). Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone] or email: [e-mail]].

8

Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 281490 (6b). Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone] or email: [e-mail]].