High Pressure-Promoted Cycloaddition Reactions of 4-Methylphenyl 1,2-Propadienyl Sulfone
H), 2.26Ϫ2.29 (m, 2 H), 2.32Ϫ2.34 (m, 2 H), 2.44 (s, 3 H), 2.49 drofuran (4 mL) and triethylamine (0.5 mL). The reaction mixture
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(dd, J ϭ 7.6 Hz, 8.7 Hz, 1 H), 2.87 (ddd, J ϭ 2.9, J ϭ 8.8, J ϭ
11.7 Hz, 1 H), 3.38 (ddd, J ϭ 2, J ϭ 7.5, J ϭ 9.4 Hz, 1 H),
was heated at 65 °C for 16 h and then concentrated in vacuo, fur-
ther purification of the residue not being necessary. Yield 12a:
3.65Ϫ3.73 (m, 4 H), 6.08 (dd, J ϭ 2.0, J ϭ 2.8 Hz, 1 H), 7.33 (d, 100 mg (100%). Oil. 1H NMR: δ ϭ 2.43 (s, 9 H), 3.93 (s, 3 H), 4.50
J ϭ 8.5 Hz, 2 H with fine splitting), 7.74 (d, J ϭ 8.3 Hz, 2 H with
(s, 1 H), 4.92 (s, 1 H), 5.60 (d, J ϭ 12.3 Hz, 1 H), 36.78 (d, J ϭ
fine splitting) ppm. 13C NMR: δ ϭ 21.4, 21.6, 26.0, 33.4, 48.9, 51.9, 12.3 Hz, 1 H), 7.31 (br. d, J ϭ 7.8 Hz, 2 H), 7.74 (br. d, J ϭ 8.4 Hz,
65.8, 66.6, 120.0, 127.1, 129.8, 139.2, 144.0, 166.7 ppm.
C18H25NO3S (335.46): calcd. C 64.45, H 7.51, N 4.18; found C
64.48, H 7.45, N 4.18.
2 H) ppm. 13C NMR: δ ϭ 21.5, 28.0, 61.2, 77.4, 109.1, 117.9, 128.4,
129.7, 132.5, 135.1, 144.5, 144.8 ppm. HRMS calcd. for
C16H22O3S: 294.1289; found 294.1283.
3,3-Dimethyl-2-methylene-4-morpholinocyclobutyl 4-Methylphenyl
Sulfone (10): Oil. 1H NMR: δ ϭ 0.96 (s, 3 H), 1.15 (s, 3 H),
2.28Ϫ2.30 (m, 2 H), 2.39Ϫ2.45 (m, 2 H), 2.45 (s, 3 H), 2.75 (d, J ϭ
6.9 Hz), 3.64Ϫ3.67 (m, 4 H), 4.35 (dt, J ϭ 2.7, J ϭ 6.9 Hz, 1 H),
5.05 (dd, J ϭ 1.0, J ϭ 3.0 Hz, 1 H), 5.17 (dd, J ϭ 1.0, J ϭ 2.5 Hz,
1 H), 7.35 (d, J ϭ 8.2, 2 H with fine coupling), 7.78 (d, J ϭ 8.3 Hz,
2 H, with fine coupling) ppm. 13C NMR: δ ϭ 21.8, 22.5, 26.9, 45.1,
52.3, 65.2, 66.5, 68.8, 109.1, 129.4, 129.7, 134.5, 144.9, 147.5 ppm.
HRMS calcd. for C18H25NO3S: 335.1555; found 335.1554.
[1]
For reviews see: [1a] P. H. Beusker, J. W. Scheeren, in: The chem-
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[2]
For recent examples of cycloadditions of electron-rich allenes
[2a]
see:
L. L. Wei, R. P. Hsung, H. Xiong, J. A. Mulder, N. T.
[2b]
Nkansah, Org. Lett. 1999, 1, 2145Ϫ2148.
M. Kimura, Y.
N-{3-Ethoxy-1-[(4-methylphenylsulfonyl)methyl]cyclobutyl}-N,N-di-
methylamine (11a): Compound 7a (100 mg, 0.38 mmol) was dis-
solved in acetonitrile (4 mL). The reaction mixture was saturated
with dimethylamine. After 5 h the reaction mixture was concen-
trated in vacuo. The residue was recrystallized from n-pentane.
Horino, Y. Wakamiya, T. Okajima, Y. Tamura, J. Am. Chem.
Soc. 1997, 119, 10869Ϫ10870. [2c] M. Hojo, K. Tomita, Y. Hiro-
hara, A. Hosomi, Tetrahedron Lett. 1993, 34, 8123Ϫ8126.
[3]
For recent examples of cycloadditions of electron-poor allenes
[3a]
see:
M. P. S. Ishar, K. Kumar, S. Kaur, N. K. Girdhar, S.
1
Yield 11a: 105 mg (90%). M.p. 75 °C. H NMR: δ ϭ 1.18 (t, J ϭ
Sachar, A. Marwaha, A. Kapoor, Org. Lett. 2001, 3,
[3b]
6.9 Hz, 3 H), 2.07 (s, 6 H), 2.07Ϫ2.17 (m, 2 H), 2.44 (s, 3 H),
2.73Ϫ2.80 (m, 2 H), 3.18 (s, 2 H), 3.41 (q, J ϭ 6.9 Hz, 2 H), 4.02
(quin, J ϭ 6.9 Hz, 1 H), 7.34 (d, J ϭ 7.8 Hz, 2 H), 7.80 (d, J ϭ
8.1 Hz, 2 H) ppm. 13C NMR: δ ϭ 15.3, 21.5, 37.1, 36.6, 55.8, 57.7,
63.3, 65.0, 127.7, 129.5, 139.0, 144.2 ppm. HRMS calcd. for
C16H25NO3S [M ϩ H]: 312.1633; found 312.1634.
2133Ϫ2136.
F. Scheufler, M. E. Maier, Eur. J. Org. Chem.
[3c]
2000, 3945Ϫ3948.
J. R. Bull, N. S. Desmond-Smith, S. J.
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3883Ϫ3890.
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A. Padwa, M. Meske, S. S. Murphree, S. H. Watterson, Z. Ni,
J. Am. Chem. Soc. 1995, 117, 7071Ϫ7080.
N-{3-(tert-Butoxy)-1-[(4-methylphenylsulfonyl)methyl]cyclobutyl}-
N,N-dimethylamine (11b): Compound 7b (100 mg, 0.34 mmol) was
dissolved in acetonitrile (4 mL). The reaction mixture was saturated
with dimethylamine. After 5 h the reaction mixture was concen-
trated in vacuo. The residue was recrystallized from n-hexane. Yield
[7a] A. J. Guilford, R. W. Turner, J. Chem. Soc., Chem. Commun.
[7b]
1983, 466Ϫ467.
K. Hayakawa, H. Nishiyama, K. Kanem-
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1146Ϫ1150, and references cited therein.
[8]
[9]
1
11b: 108 mg (94%). M.p. 100 °C. H NMR: δ ϭ 1.17 (s, 9 H), 2.05
(s, 6 H), 2.05Ϫ2.15 (m, 2 H), 2.45 (s, 3 H), 2.69Ϫ2.76 (m, 2 H),
3.19 (s, 2 H), 4.16 (quin, J ϭ 7.5 Hz, 1 H), 7.34 (d, J ϭ 7.8 Hz, 2
H), 7.81 (d, J ϭ 8.4 Hz, 2 H) ppm. 13C NMR: δ ϭ 21.5, 28.3, 37.1,
41.5, 56.0, 57.6, 58.3, 73.6, 127.7, 129.5, 139.0, 144.1 ppm. HRMS
calcd. for C18H29NO3S [M ϩ H]: 340.1946; found 340.1944.
[10]
[11]
[12]
4-Ethoxy-2-methylene-3-butenyl 4-Methylphenyl Sulfone (12a):
Compound 7a (100 mg, 0.34 mmol) was dissolved in tetrahydrofu-
ran (4 mL) and triethylamine (0.5 mL). The reaction mixture was
heated at 65 °C for 16 h and then concentrated in vacuo, further
purification of the residue not being necessary. Yield 12a: 100 mg
(100%). Oil. 1H NMR: δ ϭ 1.25 (t, J ϭ 7.2 Hz, 3 H), 2.43 (s, 3 H),
3.74 (q, J ϭ 7.2 Hz, 2 H), 3.87 (s, 2 H), 4.57 (s, 1 H), 4.99 (s, 1 H),
5.45 (d, J ϭ 12.9 Hz, 1 H), 6.57 (d, J ϭ 12.9 Hz, 1 H), 7.30 (d J ϭ
8.1 Hz, 2 H, with fine splitting), 7.74 (d, J ϭ 8.4 Hz, 2 H, with fine
splitting) ppm. 13C NMR: δ ϭ 14.7, 21.5, 61.1, 65.9, 106.2, 117.9,
128.7, 129.4, 132.1, 135.3, 144.6, 149.6 ppm. HRMS calcd. for
C14H18O3S: 266.0976; found 266.09763.
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F. Wurche, F.-G. Klärner, in: High pressure Chemistry
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Received September 25, 2002
[14]
[15]
[16]
[17]
4-(tert-Butoxy)-2-methylene-3-butenyl 4-Methylphenyl Sulfone
(12b): Compound 7b (100 mg, 0.38 mmol) was dissolved in tetrahy-
[O02524]
Eur. J. Org. Chem. 2003, 894Ϫ897
897