3990
G. Ragagnin et al. / Tetrahedron 58 ꢀ2002) 3985±3991
7
2
5 MHz): 202.6, 43.6, 33.8, 32.6, 29.1, 29.0, 28.9, 28.5,
7.9, 21.9.
22.9, 24.1, 27.0, 34.6, 38.6, 127.0, 128.7, 135.4, 154.7,
2
1
200.6; IR (n (cm ), Film): 3031 (w), 2961 (s), 2932 (m),
683 (s), 1607 (s), 1413 (m), 1184 (m), 111 (m), 844 (w);
MS (EI, 70 eV, m/e (rel. int.)): 203 (M 21), 189 (1), 162
1
.3.8. 10-Undecenal31 +3h). From 224 mg (1.9 mmol) of
h, obtained 248 mg (78%, method A). H NMR (d
1
3
2
1
(65), 161 (37), 148 (22), 147 (100), 91 (21); Anal. calcd for
2
1
(
ppm), CDCl , 300 MHz): 9.73 (t, 1H), 5.87±5.83 (m,
3
C H O (M204.21 g mol ): C: 82.3, H: 9.87, found: C:
14 20
1
H), 4.94 (d, 1H), 4.90 (d, 1H), 2.38 (td, 2H), 2.01±1.98
m, 2H), 1.60 (m, 2H), 1.31 (m, 10H); C NMR (d (ppm),
82.0, H: 9.54.
1
3
(
CDCl , 75 MHz): 202.8, 139.1, 114.2, 43.9, 33.8, 29.3, 29.2,
3.3.15. 2-Decanone +3o). From 340 mg (2.0 mmol) of 2o,
obtained 279 mg (88%, method B, 1st run). H NMR (d
3
1
2
9.1, 29.0, 28.9, 22.1.
(ppm), CDCl , 300 MHz): 0.808 (t, 3H), 1.203 (m, 10H),
1.497 (p, 2H), 2.061 (s, 3H), 2.343 (t, 2H); C NMR (d
(ppm), CDCl , 75 MHz): 209.8, 44.2, 32.2, 30.2, 29.7, 29.6,
3
3
1
3
3.3.9. Citronellal +3i). From 312 mg (2.0 mmol) of 2i,
obtained 283 mg (92%, method A). H NMR (d (ppm),
1
CDCl , 300 MHz): 9.680 (t, 1H), 5.013 (tt, 1H), 2.304 (m,
3
29.5, 24.3, 23.0, 14.5.
1
3
H), 2.173 (m, 1H), 1.939 (m, 3H), 1.612 (s, 3H), 1.531 (s,
H), 1.360±1.118 (m, 2H), 0.902 (d, 3H); C NMR (d
1
3
3.3.16. 3-Dodecanone34 +3p). From 372 mg (2.0 mmol) of
2p, obtained 254 mg (69%, method A). H NMR (d (ppm),
1
(
ppm), CDCl , 75 MHz): 202.0, 130.7, 123.0, 50.0, 35.9,
3
2
6.8, 24.7, 24.4, 18.9, 16.6.
CDCl , 300 MHz): 2.33 (t, 2H), 2.31 (q, 2H), 1.60±1.47 (m,
3
1
3
H), 1.20 (m, 12H), 0.89 (t, 3H), 0.81 (t, 3H); C NMR (d
2
(ppm), CDCl , 75 MHz): 211.0, 44.9, 42.9, 31.5, 29.6, 29.2,
23.5, 22.5, 17.4, 14.0.
3.3.10. 6-Oxohexanoic acid ethyl ester +3j). From 320 mg
2.0 mmol) of 2j, obtained 281 mg (89%, method A). H
3
1
(
NMR (d (ppm), CDCl , 300 MHz): 9.768 (t, 1H), 4.123
3
(
1
q, 2H), 2.328 (m, 2H), 2.239 (m, 2H), 1.603 (m, 4H),
3.3.17. 4-Tridecanone +3q). From 400 mg (2.0 mmol) of
2q, obtained 122 mg (31%, method A). H NMR (d
1
.252 (t, 3H); C NMR (d (ppm), CDCl , 75 MHz):
3
1
3
2
02.6, 173.9, 60.7, 44.2, 33.4, 23.8, 22.7, 14.3.
(ppm), CDCl , 300 MHz): 2.32 (t, 2H), 2.31 (t, 2H), 1.60±
3
1
3
.47 (m, 4H), 1.20 (m, 12H), 0.85 (t, 3H), 0.81 (t, 3H); C
1
NMR (d (ppm), CDCl , 75 MHz): 211.2, 44.6, 42.7, 31.8,
29.3, 29.2, 23.8, 22.6, 17.2, 14.0, 13.6.
3.3.11. 1-+1-Naphthyl)-pentanone +3k). From 435 mg
2.0 mmol) of 2k, obtained 393 mg (91%, method A). H
3
1
(
NMR (d (ppm), CDCl , 300 MHz): 8.50 (d, 1H), 7.89 (d,
3
1
1
H), 7.79±7.70 (m, 2H), 7.55±7.35 (m, 3H), 2.96 (t, 2H),
.71 (quin, 2H), 1.37 (sext, 2H), 0.87 (t, 3H); C NMR (d
3.3.18. Cyclohexanone +3r). From 200 mg (2.0 mmol) of
2r, obtained 145 mg (74%, 1st run, method A). H NMR (d
1
3
1
(
ppm), CDCl , 75 MHz): 204.9, 136.2, 133.5, 132.4, 130.0,
3
(ppm), CDCl , 300 MHz): 1.670±1.729) (m, 2H), 1.795±
3
1
1.877 (m, 4H), 2.306 (t, 4H); C NMR (d (ppm), CDCl3,
3
1
1
2
7
1
2
7
28.5, 127.9, 127.0, 126.4, 125.6, 124.1, 41.7, 26.7, 22.6,
2
1
3.9; IR (n (cm ), Film): 3049 (w), 2958 (s), 2931 (s),
75 MHz): 212.4, 42.3, 27.4, 25.3.
872 (m), 1682 (s), 1593 (w), 1508 (m), 799 (s); MS (EI,
0 eV, m/e (rel. int.)): 212 (M , 28), 170 (30), 155 (100),
1
3.3.19. Cycloheptanone +3s). From 232 mg (2.0 mmol) of
2s, obtained 186 mg (82%, method B). H NMR (d (ppm),
1
43 (13), 127 (79); Anal. calcd for C H O (M
1
5
16
2
1
12.29 g mol ): C: 84.87, H: 7.60; Found: C: 85.06, H:
.41.
CDCl , 300 MHz): 2.462±2.219 (m, 4H), 1.565±1.148 (m,
3
1
8H); C NMR (d (ppm), CDCl , 75 MHz): 213.5, 43.2,
3
3
2
7.1, 26.2.
3
.3.12. 1-Phenyl-1-hepten-3-one32 +3l). From 380 mg
2.0 mmol) of 2l, obtained 316 mg (84%, method A). H
1
(
NMR (d (ppm), CDCl , 300 MHz): 7.56±7.50 (m, 2H),
3.3.20. Cyclooctanone +3t). From 258 mg (2.0 mmol) of 2t,
obtained 215 mg (85%, method B). H NMR (d (ppm),
1
3
7
2
.54 (d, 1H), 7.33±7.28 (m, 3H), 6.72 (d, 1H), 2.64 (t,
H), 1.65 (quin, 2H), 1.37 (sext, 2H), 0.90 (t, 3H);
CDCl , 300 MHz) 2.371±2.413 (m, 4H), 1.819±1.901 (m,
3
1
3
C
13
4H), 1.492±1.571 (m, 4H), 1.321±1.369 (m, 2H); C NMR
NMR (d (ppm), CDCl , 75 MHz): 200.7, 142.4, 134.7,
3
(d (ppm), CDCl , 75 MHz): 218.6, 42.3, 27.5, 26.0, 25.1.
3
1
30.4, 129.0, 128.3, 126.4, 40.8, 26.6, 22.5, 14.0.
3
.3.21. 5-Phenyl, 5-hydroxypentanoic acid lactone35 +3u).
From 376 mg (2.1 mmol) of 2u, obtained 326 mg (89%). H
.3.13. 1-+4-Cyanophenyl)-1-pentanone33 +3m). From
1
3
3
A). H NMR (d (ppm), CDCl , 300 MHz): 0.885 (t, 3H),
78 mg (2.0 mmol) of 2m, obtained 362 mg (97%, method
NMR (d (ppm), CDCl , 300 MHz): 1.733±1.850 (m, 1H),
3
1
1.900 (m, 2H), 2.089 (dq, 1H), 2.448±2.667 (m, 2H), 5.274
3
1
3
1
7
2
.328 (p, 2H), 1.656 (p, 2H), 2.908 (t, 2H), 7.695 (d, 2H),
.968 (d, 2H); C NMR (d (ppm), CDCl , 75 MHz): 14.3,
2.7, 26.5, 39.0, 116.6, 118.4, 128.8, 132.9, 140.4, 199.4; IR
(dd, 1H), 7.273 (m, 5H); C NMR (d (ppm), CDCl3,
75 MHz): 18.8, 29.7, 30.7, 81.9, 125.9, 128.5, 128.8,
140.0, 171.6.
1
3
3
2
1
(
n (cm ), KBr): 3049 (w), 2956 (m), 2233 (m), 1686 (s),
406 (m), 1206 (m), 854 (m), 574 (w).
1
3.3.22. 4-Methylcyclohexanone +5a). From 230 mg (2.0
mmol) of 4a (47:53 cis/trans mixture), obtained 101 mg
1
(45%, method A). H NMR (d (ppm), CDCl , 300 MHz)
3
.3.14. 1-+4-Isopropylphenyl)-1-pentanone +3n). From
26 mg (2.1 mmol) of 2n, obtained 405 mg of colourless
3
4
liquid (95%, method A). H NMR (d (ppm), CDCl3,
0.775 (d, 3H), 1.169 (p, 2H), 1.571±1.708 (m, 1H),
1.709±1.804 (m, 2H), 2.077±2.122 (m, 4H); C NMR (d
1
13
3
1
2
00 MHz): 0.863 (t, 3H), 1.180 (d, 2H), 1.333 (m, 2H),
.631 (p, 2H), 2.850 (h, 1H), 2.852 (t, 2H), 2.301 (d, 2H),
.811 (d, 2H); C NMR (d (ppm), CDCl , 75 MHz): 14.3,
(ppm), CDCl , 75 MHz): 212.6, 41.2, 35.1, 31.5, 21.3; IR
3
(KBr): 2954 (m), 2929 (m), 1716 (s), 1459 (m), 1422 (m),
1121 (s), 616 (m).
1
3
3