3
Lorenzo, E.; Yus, M. J. Org. Chem. 1996, 61, 6058; d) Gilman,
A proposed mechanistic pathway of the reaction has been
presented in scheme 3. Carboxylic acid 1 reacts with DCC at
room temperature to form O-acyl isourea derivative 4. Upon
treatment of orgnolithium reagent, intermediate 4 reacts with one
molecule of RLi to produce 4a which could be in equilibrium
with 4b. Second molecule of RLi attacks on the carbonyl carbon
of 4b to yield the desired product 3 along with the urea derivative
H.; van Ess, P. R. J. Am. Chem. Soc. 1933, 55, 1258; e) Tegner, C.
Acta Chem. Scand. 1952, 6, 782; f) Jorgenson, M. J. Org. React.
970, 18, 1; g) Bare, T. M.; House, H. O. Org. Synth. 1973, 5,
75; h) Lubell, W. D.; Rapoport, H. J. Am. Chem. Soc. 1988,110,
1
7
7447; i) Levine, R.; Karten, M. J. J. Org. Chem, 1976, 41, 1176.
5. For metal catalyzed reaction: a) Amani, J.; Molander, G. A. Org.
Lett. 2017, 19, 3612; b) Fiandanese, V.; Marchese, G.; Ronzini, L.
Tetrahedron Lett. 1983, 24, 3677; c) Gooen, L. J.; Ghosh, K.
Angew. Chem. Int. Ed. 2001, 40, 3458; d) Gooen, L. J.; Ghosh,
K. Eur. J. Org. Chem. 2002, 2002, 3254; e) Kakino, R.;
Narahashi, H.; Shimizu, I.; Yamamoto, A. Chem. Lett. 2001, 30,
6
.
In conclusions, a simple one pot method for the synthesis of
ketone from carboxylic acid has been described. In this process,
aliphatic and aromatic acids were treated with DCC to form O-
acyl isourea derivatives, which upon addition of an
organolithium compound provided the desired ketones in
exclusive manner. The limitation of this process is the complete
removal of the urea derivative from the ketone. This drawback
reduced the isolated yields of the desired ketones. Further
investigations on this process using different carbon based
nucleophiles are in progress in our laboratory and will be
reported in due course.
1
242; f) Si, S.; Wang, C.; Zhang, N.; Zou, G. J. Org.
Chem., 2016, 81, 4364; g) Luca, L. D.; Giacomelli, G.; Porcheddu,
A. Org. Lett. 2001, 3, 1519.
6. Kanagani, C. O.; Kelley, D. E.; Day, B. W. Tetrahedron Lett.
2
006, 47, 6289.
7
8
.
.
a) El-Faham, A.; Albericio, F. Chem. Rev. 2011, 111, 6557; b)
Montalbetti, C. A. G. N.; Falque, V. Tetrahedron 2005, 61, 10827.
a) Valeur, E.; Bradley, M. Chem. Soc. Rev. 2009, 38, 606; b)
Selinger, Z.; Lapidot, Y. J. Lipid Research 1965, 7, 174.
9. a) Moffatt, J. G. Org. Synth. 1967, 47, 25; b) Pfitzner, K. E.;
Moffatt, J. G. J. Am. Chem. Soc. 1963, 85, 3027.
0. a) Baker, D. C.; Putt, S. R. Sythesis 1978, 478; b) Katritzky, A. R.;
Abdel-Fattah, A. A. A.; Gromova, A. V.; Witek, R.; Steel, P. J. J.
Org. Chem. 2005, 70, 9211; c) Staab, H. A.; Jost, E. Justus Liebigs
Ann. Chem. 1962, 655, 90.
1
Acknowledgments
Financial support of DST-SERB (Ref. No. SB/FT/CS-
49/2013) is acknowledged. HGM appreciates the support of
Govt. of Ethiopia for a research fellowship. Both of the authors
thank KIIT, Deemed to be University for providing the basic
research facility.
11. a) Neises, B.; Steglich, W. Org. Synth. 1985, 63: 183; b) Neises,
B.; Steglich, W. Angew. Chem. Int. Ed. 1978, 17, 522;
0
1
2. General Experimental procedure: To
carboxylic acid 1 (1 mmol) in THF (3 mL), DCC (1 mmol) was
added at room temperature under N atmosphere. After 1 h, the
a stirred solution of
2
mixture was cooled to -20 °C and n-BuLi (2 mmol) was added to
the reaction mixture drop-wise. After 0.5 h the reaction was
4
quenched with saturated NH Cl solution (5 mL) at -20 ºC. The
References and notes
mixture was warmed to room temperature and extracted with
diethyl ether (50 mL × 3). The combined organic layers were
washed with water (20 mL × 3), brine (20 mL) and finally dried
over MgSO . The volatiles were evaporated under reduced
4
pressure to get a crude mass which was then purified by column
1
.
a) Dieter, R. K. Tetrahedron 1999, 55, 4177; b) Lawrence, N. J. J
Chem. Soc., Perkin Trans.1 1998, 1739; c) McDaniel, R.;
.
Thamchaipenet, A.; Gustafsson, C.; Fu, H.; Betlach, M.; Betlach,
M.; Ashley, G. Proc. Natl. Acad. Sci. U. S. A. 1999, 96, 1846; d)
Cuquerella, M. C.; Lhiaubet-Vallet, V.; Cadet, J.; Miranda, M. A.
Acc. Chem. Res. 2012, 45, 1558; e) Kamat, P. V. Chem. Rev.
chromatography on silica gel to obtain pure ketone 3.
1
993, 93, 267.
2
.
Few important references are: a) Sibi, M. P. Org. Prep. Proceed.
Int. 1993, 25, 15; b) O’ Neil, B. T. In Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Schreiber, S. L., Eds.;
Pergamon Press: Oxford, 1991; Vol. 1, pp 399; c) Wilkinson, M.
C. Org. Lett. 2011, 13, 2232; d) Park, A.; Park, K.; Kim, Y.; Lee,
S. Org. Lett. 2011, 13, 944; e) Gooβen, L.; Rodriguez, N.;
Supplementary Material
Supplementary material is available
3
4
.
.
Qu, B.; Collum, D. B. J. Org. Chem. 2006, 71, 7117.
a) Rubottom, G. M.; Kim, C-W. J. Org. Chem. 1983, 48, 1550; b)
Genna, D. T.; Posner, G. Org. Lett. 2011, 13, 5358.; c) Alonso, F.;
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