A new mild method for the C-acylation of ketone enolates. a convenient synthesis of β-keto-esters,-thionoesters, and-thioesters

Organic Letters

Volumn 15, Issue 2, 2013, Pages 370-373

  Hale, Karl J ^a   Grabski, Milosz ^a   Flasz, Jakub T ^a  

^a QUEEN'S UNIVERSITY BELFAST   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84872569214     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol303324a     Document Type: Article

References (24)

1. For a previous report on the use of LiTMP and an alkyl chloroformate for the C-acylation of ketones, see: Olofson, R. A.; Cuomo, J.; Bauman, B. A. J. Org. Chem. 1978, 43, 2073
2. For examples of the use of acid chlorides to C-acylate Li-enolates, see: Wiles, C.; Watts, P.; Haswell, S.; Pombo-Villar, E. Tetrahedron Lett. 2002, 43, 2945
3. For examples of the use of acyl imidazolides to C-acylate (or O-acylate) ketone enolates, see: Trost, B. M.; Xu, J. J. Org. Chem. 2007, 72, 9372
4. Mander, L.; Sethi, S. P. Tetrahedron Lett. 1983, 24, 5425
5. Hutt, O. E.; Mander, L. N. J. Org. Chem.. 2007, 72, 10130
6. For a recent example of the use of LDA and MeOC(O)CN in THF/DMPU for a ketone kinetic enolization and C-acylation, see: Henderson, J. A.; Phillips, A. J. Angew. Chem., Int. Ed. 2008, 47, 8499
7. For the use of LDA/THF/HMPA and Mander's reagent for ketone C-acylation, see: Beshore, D. C.; Smith, A. B., III. J. Am. Chem. Soc. 2007, 129, 4148
8. For another successful use of LDA/Mander's reagent/THF at-78 C, see: Clive, D. L. J.; Sannigrahi, M.; Hisaindee, S. J. Org. Chem. 2001, 66, 954
9. For the concurrent occurrence of competing O-acylation during an attempted enolate C-acylation with MeOC(O)CN, see: Mander, L. N.; Thomson, R. J. Org. Chem. 2005, 70, 1651
10. Flasz, J. T.; Hale, K. J. Org. Lett. 2012, 14, 3024
11. For the recent documentation of cyanohydrin byproducts being formed as major reaction products during a KHMDS-mediated ketone enolization and C-acylation with MeOC(O)CN, see: Kazimierski, A.; Kałuža, Z.; Chmielewski, M. ARKIVOC 2004, 3, 213
12. Lim, D.; Fang, F.; Zhou, G.; Coltart, D. Org. Lett. 2007, 9, 4139
13. Zhou, G.; Lim, D.; Coltart, D. M. Synthesis 2009, 56
14. Manaviazar, S.; Frigerio, M.; Bhatia, G. S.; Hummersone, M. G.; Aliev, A. E.; Hale, K. J. Org. Lett. 2006, 8, 4477
15. Sato, M.; Ban, H.; Uehara, F.; Keneko, C. Chem. Commun. 1996, 775
16. 3SiH/Pd(0)-thioester reduction: Fukuyama, T.; Lin, S.-C.; Li, L. J. Am. Chem. Soc. 1990, 112, 7050
17. Liebeskind, L. S.; Srogl, J. J. Am. Chem. Soc. 2000, 122, 11260
18. Nicolaou, K. C.; McGarry, D. G.; Somers, P. K.; Veale, C. A.; Furst, G. T. J. Am. Chem. Soc. 1987, 109, 2504
19. Nicolaou, K. C.; Satao, M.; Theodorakis, E. A.; Miller, N. D. J. Chem. Soc., Chem. Commun. 1995, 1583
20. Mohr, J. T.; Behenna, D. C.; Harned, A. M.; Stoltz, B. M. Angew. Chem., Int. Ed. 2005, 44, 6924
21. Trost, B. M.; Xu, J. J. Am. Chem. Soc. 2005, 127, 17180
22. Franckevicius, V.; Cuthbertson, J. D.; Pickworth, M.; Pugh, D. S.; Taylor, R. J. K. Org. Lett. 2011, 13, 4264
23. For DMAP mechanisms for O-acylation, see: Xu, S.; Held, I.; Kempf, B.; Mayr, H.; Steglich, W.; Zipse, H. Chem.-Eur. J. 2005, 11, 4751
24. Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989