S. H. Kim et al. / Tetrahedron Letters 50 (2009) 6256–6260
6259
V.; De Vos, D. E.; Jacobs, P. A. Angew. Chem., Int. Ed. 1997, 36, 2661–2663; (c)
Park, D. Y.; Gowrisankar, S.; Kim, J. N. Tetrahedron Lett. 2006, 47, 6641–6645.
and further references cited therein.
and diallyl compound 9 (19%). As the last examination, we tried the
reaction of p-nitrobenzyl derivative 10,3b as shown in Scheme 4.
The reaction produced protonation product 11 (70%) along with
cyclohexene derivative 12 (13%) and allyl compound 13 (3%).
In summary, we synthesized various cycloalkanone derivatives
having –CH2EWG moiety at the b-position from 2-cycloalken-1-
8. Typical procedure for the synthesis of 4a and 5a (condition D): a mixture of 2-
cyclopenten-1-one (1a, 165 mg, 2.0 mmol), allyl acetoacetate (2a, 429 mg,
3.0 mmol), and K2CO3 (138 mg, 1.0 mmol) in CH3CN (5 mL) was stirred at room
temperature for 24 h. After the usual aqueous extractive workup and column
chromatographic purification process (hexanes/EtOAc, 4:1) compound 3a was
isolated as colorless oil, 356 mg (79%) as a syn/anti mixture (1:1). A mixture of
compound 3a (224 mg, 1.0 mmol), Pd(OAc)2 (12 mg, 5 mol %), PPh3 (27 mg,
10 mol %), Et3N (132 mg, 1.3 mmol), in aqueous CH3CN (H2O/CH3CN = 1:9,
3 mL) was heated to reflux under nitrogen atmosphere for 2 h. After the usual
aqueous extractive workup and column chromatographic purification
process (hexanes/EtOAc/CH2Cl2, 8:2:1) compounds 4a (100 mg, 71%) and 5a
(22 mg, 16%) were isolated as colorless oils. Other compounds were
synthesized similarly and the representative spectroscopic data of selected
compounds 4a,9j 4f, 5a,9d 5b, 5e, 5h, 6d, 6e, 6f, 8, 9, and 12 are as follows.
Known compounds were identified by comparison their spectroscopic data
with the reported, 4b,6d,g 4c,9i 4d,9c 4e,9k 4g,9a,6b 4h,6b 5d,9h 5g,9b,f 7g,9a 7h,9l
10,3b 11,3b 13.3b
ones by using
a combination of a base-catalyzed conjugate
addition with allyl ester and a Pd-catalyzed decarboxylative
protonation. Interestingly, cycloalkenone derivatives were formed
in some cases via the Pd(0)-catalyzed intramolecular redox
reaction.
Acknowledgements
This work was supported by National Research Foundation of
Korea Grant funded by the Korean Government (2009-0070633).
Spectroscopic data were obtained from the Korea Basic Science
Institute, Gwangju branch.
Compound 4a:9j 71%; colorless oil; IR (film) 1741, 1712 cmꢀ1 1H NMR (CDCl3,
;
300 MHz) d 1.44–1.59 (m, 1H), 1.74–1.85 (m, 1H), 1.96–2.69 (m, 7H), 2.17 (s,
3H); 13C NMR (CDCl3, 75 MHz) d 29.21, 30.19, 32.17, 38.21, 44.59, 48.91,
207.14, 218.59; ESIMS m/z 140 (M++1).
Compound 4f: 61%; yellow oil; IR (film) 2244, 1699 cmꢀ1 1H NMR (CDCl3,
;
300 MHz) d 1.38–1.73 (m, 3H), 1.90–2.19 (m, 4H), 2.30–2.65 (m, 6H); 13C NMR
(CDCl3, 75 MHz) d 23.70, 25.15, 27.83, 33.04, 36.00, 43.75, 48.62, 117.87,
211.46; ESIMS m/z 151 (M++1). Anal. Calcd for C9H13NO: C, 71.49; H, 8.67; N,
9.26. Found: C, 71.67; H, 8.88; N, 9.12.
References and notes
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Minami, I.; Yuhara, M.; Nisar, M.; Shimizu, I. J. Org. Chem. 1987, 52, 2988–2995;
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5246–5248; (f) Imao, D.; Itoi, A.; Yamazaki, A.; Shirakura, M.; Ohtoshi, R.;
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Chem., Int. Ed. 2005, 44, 6924–6927.
3. For our recent Letters on Pd-catalyzed decarboxylative protonation and
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Tetrahedron Lett. 2008, 49, 6241–6244; (b) Kim, S. H.; Lee, H. S.; Kim, S. H.;
Kim, J. N. Tetrahedron Lett. 2009, 50, 3038–3041; (c) Kim, J. M.; Kim, S. H.; Lee,
H. S.; Kim, J. N. Tetrahedron Lett. 2009, 50, 1734–1737.
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N.; Taylor, R. E. Angew. Chem., Int. Ed. 2004, 43, 1728–1730; (b) Julian, L. D.;
Newcom, J. S.; Roush, W. R. J. Am. Chem. Soc. 2005, 127, 6186–6187; (c) Panek, J.
S.; Jain, N. F. J. Org. Chem. 1998, 63, 4572–4573; (d) Nicolaou, K. C.; Harrison, S.
T. J. Am. Chem. Soc. 2007, 129, 429–440; (e) Gillingham, D. G.; Hoveyda, A. H.
Angew. Chem., Int. Ed. 2007, 46, 3860–3864; (f) Dias, L. C.; de Sousa, M. A.
Tetrahedron Lett. 2003, 44, 5625–5628; (g) Zheng, Y.; Avery, M. A. Tetrahedron
2004, 60, 2091–2095.
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Scafato, P.; Nardiello, M.; Casarini, D.; Giorgio, E.; Rosini, C. Tetrahedron 2004, 60,
4975–4981; (b) Superchi, S.; Nardiello, M.; Donnoli, M. I.; Scafato, P.; Menicagli,
R.; Rosini, C. C. R. Chemie 2005, 8, 867–874; (c) Kiyota, H.; Higashi, E.; Koike, T.;
Oritani, T. Tetrahedron: Asymmetry 2001, 12, 1035–1038; (d) Chapuis, C.;
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Sarkar, T. K.; Mukherjee, B.; Ghosh, S. K. Tetrahedron 1998, 54, 3243–3254; (f)
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A.; Vidari, G.; Zanoni, G. J. Org. Chem. 2005, 70, 4876–4878.
6. For the synthesis of cyclic 1,5-dicarbonyl compounds, see: (a) Shen, Z.-L.; Ji, S.-
J.; Loh, T.-P. Tetrahedron Lett. 2005, 46, 507–508; (b) Loh, T. P.; Wei, L. L.
Tetrahedron 1998, 54, 7615–7624; (c) RajanBabu, T. V. J. Org. Chem. 1984, 49,
2083–2089; (d) Sato, T.; Wakahara, Y.; Otera, J.; Nozaki, H. Tetrahedron 1991,
47, 9773–9782; (e) Matsuda, I.; Murata, S.; Izumi, Y. J. Org. Chem. 1980, 45, 237–
240; (f) Schmoldt, P.; Mattay, J. Synthesis 2003, 1071–1078; (g) Yamaguchi, M.;
Shiraishi, T.; Hirama, M. J. Org. Chem. 1996, 61, 3520–3530. and further
references cited therein; (h) Simoni, D.; Rossi, M.; Rondanin, R.; Baruchello, R.;
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Donati, D. Tetrahedron Lett. 2005, 46, 759–762; (i) Kim, S.; Han, W. S.; Lee, J. M.
Bull. Korean Chem. Soc. 1992, 13, 466–467; Further examples on Mukaiyama-
Michael type reaction, see: (j) Harada, T.; Kusukawa, T. Synlett 2007, 1823–
1835; (k) Takahashi, A.; Yanai, H.; Taguchi, T. Chem. Commun. 2008, 2385–
2387; (l) Jung, M. E.; Perez, F. Org. Lett. 2009, 11, 2165–2167; (m) Yang, H.; Kim,
S. Synlett 2008, 555–560; (n) Sartori, A.; Curti, C.; Battistini, L.; Burreddu, P.;
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11705.
Compound 5a:9d 16%; colorless oil; IR (film) 1714, 1261, 1099 cmꢀ1 1H NMR
;
(CDCl3, 300 MHz) d 1.93 (dd, J = 18.9 and 2.4 Hz, 1H), 2.19 (s, 3H), 2.57–2.74 (m,
3H), 3.35–3.45 (m, 1H), 6.18 (dd, J = 5.7 and 2.1 Hz, 1H), 7.64 (d, J = 5.7 and
2.4 Hz, 1H); 13C NMR (CDCl3, 75 MHz) d 30.11, 36.44, 41.00, 47.90, 134.35,
166.98, 206.09, 209.01; ESIMS m/z 138 (M++1). Anal. Calcd for C8H10O2: C,
69.54; H, 7.30. Found: C, 69.67; H, 7.43.
Compound 5b: 12%; colorless oil; IR (film) 1714, 1678 cmꢀ1 1H NMR (CDCl3,
;
300 MHz) d 1.86–2.79 (m, 7H), 2.16 (s, 3H), 6.02–6.07 (m, 1H), 6.92–6.98 (m,
1H); 13C NMR (CDCl3, 75 MHz) d 30.46 (2C), 31.53, 43.86, 48.67, 129.75, 149.24,
198.83, 206.65; ESIMS m/z 152 (M++1). Anal. Calcd for C9H12O2: C, 71.03; H,
7.95. Found: C, 71.24; H, 8.03.
Compound 5e: 14%; colorless oil; IR (film) 2247, 1682, 1429 cmꢀ1 1H NMR
;
(CDCl3, 300 MHz) d 2.27–2.65 (m, 7H), 6.07–6.14 (m, 1H), 6.95–7.02 (m, 1H);
13C NMR (CDCl3, 75 MHz) d 23.24, 30.72, 31.90, 43.00, 117.21, 130.00, 147.78,
196.83; ESIMS m/z 135 (M++1). Anal. Calcd for C8H9NO: C, 71.09; H, 6.71; N,
10.36. Found: C, 71.34; H, 6.54; N, 10.12.
Compound 5h: 4%; colorless oil; IR (film) 1731, 1681, 1259 cmꢀ1 1H NMR
;
(CDCl3, 300 MHz) d 1.27 (t, J = 7.2 Hz, 3H), 2.01–2.68 (m, 7H), 4.15 (q, J = 7.2 Hz,
2H), 6.03–6.07 (m, 1H), 6.93–6.99 (m, 1H); 13C NMR (CDCl3, 75 MHz) d 14.21,
31.50, 31.83, 39.98, 43.80, 60.61, 129.78, 149.10, 171.56, 198.65; ESIMS m/z
182 (M++1). Anal. Calcd for C10H14O3: C, 65.91; H, 7.74. Found: C, 65.86; H, 7.55.
Compound 6d: 31% (1:1 mixture); yellow oil; IR (film) 2239, 1743, 1406 cmꢀ1
;
1H NMR (CDCl3, 300 MHz) d 1.72–1.85 (m, 1H), 1.97–2.55 (m, 8H), 2.70–2.80
(m, 1H), 5.21–5.28 (m, 2H), 5.76–5.92 (m, 1H); 13C NMR (CDCl3, 75 MHz) d
26.77, 27.66, 34.86, 35.08, 36.50, 36.52, 37.99, 38.05, 38.19, 38.29, 41.66, 42.93,
119.33, 119.36, 119.65, 119.70, 132.51, 132.58, 215.60, 215.72; ESIMS m/z 163
(M++1). Anal. Calcd for C10H13NO: C, 73.59; H, 8.03; N, 8.58. Found: C, 73.43; H,
8.35; N, 8.29.
Compound 6e: 23% (1:1 mixture); yellow oil; IR (film) 2237, 1714, 1448 cmꢀ1
;
1H NMR (CDCl3, 300 MHz) d 1.53–1.78 (m, 2H), 1.84–2.74 (m, 10H), 5.18–5.26
(m, 2H), 5.71–5.87 (m, 1H); 13C NMR (CDCl3, 75 MHz) d 24.42, 24.51, 27.30,
29.86, 33.78, 33.89, 37.42, 37.51, 39.23, 39.32, 40.90, 40.95, 43.49, 46.09,
119.25, 119.27, 119.58, 119.68, 132.60, 132.64, 209.00, 209.09; ESIMS m/z 177
(M++1). Anal. Calcd for C11H15NO: C, 74.54; H, 8.53; N, 7.90. Found: C, 74.61; H,
8.76; N, 7.87.
Compound 6f: 29% (1:1 mixture); yellow oil; IR (film) 2237, 1701, 1447 cmꢀ1
;
1H NMR (CDCl3, 300 MHz) d 1.32–1.77 (m, 3H), 1.86–2.07 (m, 4H), 2.27–2.77
(m, 7H), 5.18–5.26 (m, 2H), 5.72–5.86 (m, 1H); 13C NMR (CDCl3, 75 MHz) d
23.79 (2C), 27.75, 28.11, 32.58, 33.97, 34.11, 35.74, 36.89, 37.21, 38.24, 38.35,
43.65, 43.72, 45.34, 48.21, 119.21, 119.24, 119.85, 119.87, 132.74, 132.76,
211.85, 211.88; ESIMS m/z 191 (M++1). Anal. Calcd for C12H17NO: C, 75.35; H,
8.96; N, 7.32. Found: C, 75.42; H, 9.10; N, 7.23.
Compound 8: 29% (1:1 mixture); yellow oil; IR (film) 1743, 1709, 1357 cmꢀ1
;
1H NMR (CDCl3, 300 MHz) d 1.45–1.62 (m, 1H), 1.78–1.96 (m, 1H), 2.05–2.65
*
*
(m, 8H), 2.14 (s, 3H 0.5), 2.17 (s, 3H 0.5), 5.02–5.17 (m, 2H), 5.62–5.78 (m, 1H);
13C NMR (CDCl3, 75 MHz) d 27.40, 28.09, 30.48, 30.70, 34.09, 35.28, 37.92,
38.28, 38.43, 38.50, 42.96, 43.36, 57.61, 57.97, 117.53 (2C), 134.30, 134.38,
210.66, 210.77, 217.54, 217.72; ESIMS m/z 180 (M++1).
Compound 9: 19%; yellow oil; IR (film) 1743, 1698, 1355 cmꢀ1 1H NMR (CDCl3,
;
300 MHz) d 1.66–1.81 (m, 1H), 2.04–2.20 (m, 3H), 2.18 (s, 3H), 2.24–2.59 (m,
7H), 5.09–5.19 (m, 4H), 5.66–5.81 (m, 2H); 13C NMR (CDCl3, 75 MHz) d 24.54,
28.29, 37.90, 38.08, 38.53, 40.46, 42.41, 55.27, 118.69, 118.73, 133.46 (2C),
211.36, 217.62; ESIMS m/z 220 (M++1).
Compound 12: 13%; yellow oil; IR (film) 1678, 1517, 1345 cmꢀ1 1H NMR
;
(CDCl3, 300 MHz) d 2.04–2.54 (m, 5H), 2.81 (d, J = 6.6 Hz, 2H), 6.04–6.08 (m,
1H), 6.91–6.97 (m, 1H), 7.32 (d, J = 8.7 Hz, 2H), 8.18 (d, J = 9.0 Hz, 2H); 13C NMR
(CDCl3, 75 MHz) d 31.62, 36.63, 41.69, 43.86, 123.80, 129.81, 130.00, 146.79,
7. For the synthesis of starting materials by Michael addition, see: (a) Ye, W.; Xu,
J.; Tan, C.-T.; Tan, C.-H. Tetrahedron Lett. 2005, 46, 6875–6878; (b) Subba Rao, Y.