4234
H. Miyabe et al. / Tetrahedron 60 (2004) 4227–4235
colorless oil. IR (CHCl3) 2963, 1781, 1697 cm21. 1H NMR
(CDCl3) d 4.41 (2H, t, J¼8.3 Hz), 4.02 (2H, t, J¼8.3 Hz),
2.95 (1H, dd, J¼16.2, 5.1 Hz), 2.74 (1H, dd, J¼16.2,
9.3 Hz), 2.04–1.94 (1H, m), 1.69–1.58 (1H, m), 0.91 (3H,
d, J¼6.6 Hz), 0.87 (3H, d, J¼6.6 Hz) 0.89 (3H, d,
J¼6.9 Hz). 13C NMR (CDCl3) d 173.4, 153.4, 61.8, 42.5,
39.4, 35.0, 32.1, 19.9, 18.1, 15.6. HRMS Calcd for
C10H17NO3 (Mþ) 199.1207, found 199.1203.
4.7.1. 3-Methylbutyl phenyl sulfone (27a). A white solid.
1
IR (CHCl3) 2961 1469, 1448 cm21. H NMR (CDCl3) d
7.93–7.55 (5H, m), 3.11–3.06 (2H, m), 1.63–1.58 (3H, m),
0.87 (6H, d, J¼6.6 Hz). 13C NMR (CDCl3) d 139.1, 133.5,
129.2, 127.9, 54.6, 30.9, 27.1, 21.9. HRMS Calcd for
C11H16O2S (Mþ) 212.0870, found 212.0879.
4.7.2. 3-Methylpentyl phenyl sulfone (27b). A colorless
1
oil. IR (CHCl3) 3028, 2964, 1587, 1464, 1448 cm21. H
4.6.3. 3-[(4-Methyl-3-phenyl)pentanoyl]-2-oxazolidine
(24c). A colorless oil. IR (CHCl3) 3028, 2963, 2927,
NMR (CDCl3) d 7.93–7.55 (5H, m), 3.17–3.00 (2H, m),
1.79–1.07 (5H, m), 0.85–0.80 (6H, m). 13C NMR (CDCl3)
d 139.1, 133.5, 129.2, 128.0, 54.4, 33.4, 28.8, 28.7, 18.6,
11.0. HRMS Calcd for C12H18O2S (Mþ) 226.1026, found
226.1027.
1
1780, 1701, 1494, 1481 cm21. H NMR (CDCl3) d 7.31–
7.14 (5H, m), 4.37–4.15 (2H, m), 3.91–3.73 (2H, m), 3.53
(1H, dd, J¼16.5, 10.2 Hz), 3.21 (1H, dd, J¼16.5, 4.8 Hz),
2.98 (1H, ddd, J¼10.2, 8.2, 4.8 Hz), 1.96–1.85 (1H, m),
0.99 (3H, d, J¼6.6 Hz), 0.75 (3H, d, J¼6.6 Hz). 13C NMR
(CDCl3) d 172.6, 153.5, 143.0, 128.4, 128.0, 126.3, 61.9,
48.5, 42.5, 38.6, 33.2, 20.7, 20.5. HRMS Calcd for
C15H19NO3 (Mþ) 261.1363, found 261.1368.
4.7.3. 2-Cyclopentylethyl phenyl sulfone (27c). Colorless
crystals. Mp 68–69 8C (AcOEt/hexane). IR (CHCl3) 3028,
1
2954, 1587, 1448 cm21. H NMR (CDCl3) d 7.93–7.55
(5H, m), 3.13–3.07 (2H, m), 1.74–1.69 (5H, m), 1.58–1.50
(4H, m), 1.08–1.02 (2H, m). 13C NMR (CDCl3) d 139.2,
133.6, 129.2, 128.0, 55.7, 38.7, 32.2, 28.5, 25.0. HRMS
Calcd for C13H18O2S (Mþ) 238.1026, found 238.1024.
Anal. Calcd for C13H18O2S: C, 65.51; H, 7.61; S, 13.45.
Found: C, 65.43; H, 7.47; S, 13.73.
4.6.4. N-(2-Hydroxyethyl)-4-methyl-N-(phenylmethyl)-
pentanoylamide (25). The presence of rotamers (3:1)
precluded a comprehensive assignment of all proton
resonances. A colorless oil. IR (CHCl3) 3393, 3008, 2960,
1626, 1469 cm21. 1H NMR (CDCl3) d 7.40–7.17 (5H, m),
4.67 (2/4H, s), 4.61 (6/4H, s), 3.75–3.69 (2H, m), 3.56
(6/4H, t, J¼4.5 Hz), 3.42 (2/4H, t, J¼4.5 Hz), 2.59 (1H, br
s), 2.48 (2/4H, t, J¼7.5 Hz), 2.38 (6/4H, t, J¼7.5 Hz), 1.62–
1.53 (3H, m), 0.98 (3H, d, J¼6.3 Hz), 0.86 (3H, d,
J¼6.3 Hz). 13C NMR (CDCl3) d 176.3, 174.3, 137.9,
136.4, 129.0, 128.6, 127.9, 127.8, 127.3, 126.3, 62.3, 60.1,
52.7, 50.0, 49.0, 48.5, 34.3, 34.1, 31.3, 27.9, 27.8, 22.4,
22.3. HRMS Calcd for C15H23NO2 (Mþ) 249.1727, found
249.1725.
4.7.4. 3,3-Dimethylbutyl phenyl sulfone (27d). Colorless
crystals. Mp 60–60.5 8C (AcOEt/hexane). IR (CHCl3)
.
3027, 2962, 1587, 1476, 1448, 1303, 1150 cm21 1H
NMR (CDCl3) d 7.93–7.56 (5H, m), 3.09–3.04 (2H, m),
1.63–1.57 (2H, m), 0.87 (9H, s). 13C NMR (CDCl3) d 139.2,
133.6, 129.2, 128.0, 52.9, 35.6, 30.0, 28.9. HRMS Calcd for
C12H18O2S (Mþ) 226.1026, found 226.1011. Anal. Calcd
for C12H18O2S: C, 63.68; H, 8.02; S, 14.17. Found: C,
63.64; H, 7.86; S, 13.93.
4.6.5. N-(2-Butenyl)-4-methyl-N-phenylmethylpenta-
noylamide (26). The presence of rotamers (1:1 (Z-isomer),
2:3 (E-isomer)) precluded a comprehensive assignment of
1H and 13C NMR. A colorless oil. IR (CHCl3) 3019, 2960,
1630 cm21. 1H NMR (CDCl3) d 7.35–7.15 (5H, m), 5.65–
5.31 (2H, m), 4.57 (4/7H (Z)þ4/7H (E), br s), 4.49 (6/7H
(E), br s), 4.05 (2/7H (Z), br d, J¼7.2 Hz), 3.93 (4/7H (E), br
d, J¼5.7 Hz), 3.85 (2/7H (Z), br d, J¼6.6 Hz), 3.74 (6/7H
(E), br d, J¼5.1 Hz), 2.40–2.30 (2H, m), 1.72–1.54 (6H,
m), 0.92 (24/7H, d, J¼5.7 Hz), 0.85 (18/7H, d, J¼5.7 Hz).
13C NMR (CDCl3) d 173.6, 137.9, 137.1, 129.0, 128.8,
128.5, 128.2, 127.6, 127.4, 127.1, 126.4, 126.3, 125.9,
125.6, 50.2, 49.9, 48.5, 48.1, 47.8, 47.2, 43.8, 41.6, 34.3,
31.3, 31.2, 29.7, 27.9, 27.8, 22.4, 22.3, 17.7, 17.6, 12.9.
HRMS Calcd for C17H25NO (Mþ) 259.1935, found
259.1937.
Acknowledgements
We wish to thank Grant-in Aid for Scientific Research (B)
from the Japan Society for the Promotion of Science and the
Science Research Promotion Fund of the Japan Private
School Promotion Foundation for research grants.
References and notes
1. Garner, P. P.; Parker, D. T.; Gajewski, J. J.; Lubineau, A.;
´
Ange, J.; Queneau, Y.; Beletskaya, I. P.; Cheprakov, A. V.;
Fringuelli, F.; Piermatti, O.; Pizzo, F.; Kobayashi, S. In
Organic synthesis in water; Grieco, P. A., Ed.; Blackie
Academic and Professional: London, 1998.
4.7. General procedure for the radical addition to 20
2. For reviews, see: (a) Li, C. J. Chem. Rev. 1993, 93, 2023.
To a micro tube containing 20 (95% of purity, 50 mg,
0.282 mmol), RI (1.41 mmol), indium (280 mg,
1.97 mmol), and MeOH (0.2 mL) was added dropwise
H2O (0.8 mL) at 20 8C over 5 min. After being stirred at the
same temperature for 30 min, the reaction mixture was
diluted with H2O and then extracted with CH2Cl2. The
organic phase was washed, dried over MgSO4, and
concentrated at reduced pressure. Purification of the residue
by preparative TLC (hexane/AcOEt 5:1) afforded 27a-d.
´
(b) Lubineau, A.; Ange, J.; Queneau, Y. Synthesis 1994, 741.
(c) Li, C. J. Tetrahedron 1996, 52, 5643.
3. For a recent review, see: (a) Li, C. J.; Chan, T. H. Tetrahedron
1999, 55, 11149. For some examples of indium-mediated
reaction, see: (b) Yang, Y.; Chan, T. H. J. Am. Chem. Soc.
2000, 122, 402. (c) Chan, T. H.; Yang, Y. J. Am. Chem. Soc.
1999, 121, 3228. (d) Paquette, L. A.; Rothhaar, R. R. J. Org.
Chem. 1999, 64, 217. (e) Woo, S.; Sqires, N.; Fallis, A. G. Org.
Lett. 1999, 1, 573. (f) Engstrom, G.; Morelli, M.; Palomo, C.;