T. Mukaiyama et al.
1
3
29.1, 137.0, 137.5, 137.8, 138.5, 142.5, 142.8, 173.6, 174.8; IR (neat): n˜ =
2-[1-(4-Chlorophenyl)-1-tosylaminomethyl]cyclohexanone
(anti-3bg):
White powder; m.p. 148.08C; H NMR: d=1.57–2.08 (m, 6H), 2.22–2.37
m, 5H), 2.72 (dt, J=5.3, 10.5 Hz, 1H), 4.43 (dd, J=5.1, 8.0 Hz, 1H),
6.20 (d, J=8.0 Hz, 1H), 6.98–7.10 (m, 6H), 7.45 (d, J=8.2 Hz, 2H);
À1
1
241, 2981, 2953, 1739, 1452 cm
.
(
S-tert-butyl 2-methyl-3-phenyl-3-(tosylamino)propanethioate (anti-3ad):
White powder; m.p. 185.08C; H NMR: d=1.14 (d, J=6.9 Hz, 3H), 1.33
1
1
3
C NMR: d=21.4, 24.4, 27.9, 32.1, 42.4, 56.4, 58.5, 126.8, 127.9, 128.5,
(
s, 9H), 2.31 (s, 3H), 2.26 (s, 3H), 2.82 (dq, J=5.9, 6.9 Hz, 1H), 4.48 (dd,
1
29.0, 132.7, 137.2, 137.3, 142.9, 212.2; IR (neat): n˜ = 3243, 2942, 2863,
J=5.9, 8.6 Hz, 1H), 5.97(d, J=8.6 Hz, 1H), 6.98–7.14 (m, 7H), 7.49 (d,
J=8.1 Hz, 2H); C NMR: d=16.4, 21.5, 29.5, 48.7, 53.5, 60.7, 126.5,
1
2
À1
1
3
1704, 1600, 1490, 1153 cm ; HRMS: m/z: calcd for C20
3
H
21ClNO
3
S:
À
90.0931; found: 390.0951 [MÀH] .
26.8, 127.2, 128.1, 129.0, 137.8, 138.8, 142.6, 203.4; IR (neat): n˜ = 3280,
À1
2-[1-(4-Cyanophenyl)-1-tosylaminomethyl]cyclohexanone
(anti-3gg):
963, 1714, 1666, 1449, 1362, 1319, 1160 cm
.
1
White powder; m.p. 141.08C; H NMR: d=1.54–2.38 (m, 10H), 2.72–2.82
m, 1H), 4.42–4.52 (m, 1H), 6.16–6.28 (m, 1H), 7.10 (d, J=8.1 Hz, 2H),
.22 (d, J=8.1 Hz, 2H), 7.39 (d, J=8.1 Hz, 2H), 7.49 (d, J=8.1 Hz, 2H);
S-tert-butyl 2-methyl-3-phenyl-3-(tosylamino)propanethioate (syn-3ad):
White powder; m.p. 145.08C; H NMR: d=1.20 (d, J=7.0 Hz, 3H), 1.23
(
1
7
(
s, 9H), 2.33 (s, 3H), 2.81 (dq, J=7.0, 7.8 Hz, 1H), 4.41 (t, J=7.8 Hz,
13
C NMR: d=21.5, 24.7, 27.9, 32.5, 42.7, 56.4, 58.8, 110.7, 118.4, 126.8,
1
8
1
1
H), 5.59 (bs, 1H), 6.97–6.98 (m, 2H), 7.06–7.11 (m, 5H), 7.51 (d, J=
1
2
27.9, 128.0, 129.2, 131.7, 143.3, 144.6, 211.9; IR (KBr): n˜ = 3278, 2943,
1
3
.1 Hz, 2H); C NMR: d=14.3, 21.5, 29.4, 48.2, 54.2, 60.3, 127.1, 127.2,
À1
866, 2227, 1699, 1434, 1337, 1160 cm
.
27.3, 127.9, 129.1, 137.0, 138.2, 142.9, 201.7; IR (neat): n˜ = 3249, 2970,
À1
2-[1-(4-Nitrophenyl)-1-tosylaminomethyl]cyclohexanone
(anti-3cg):
White powder; m.p. 175.08C; H NMR: d=1.58–2.34 (m, 11H), 2.74–2.84
m, 1H), 4.48 (dd, J=4.1, 8.4 Hz, 1H), 6.13 (d, J=8.4 Hz, 1H), 7.09 (d,
734, 1676, 1559, 1507, 1456, 1161 cm
;
HRMS: m/z: calcd for
1
À
C
21
H
26NO
3
S
2
: 404.1354; found: 404.1398 [MÀH] .
-Methyl-1,3-diphenyl-3-(tosylamino)propan-1-one (anti-3ae): White
(
2
J=8.1 Hz, 2H), 7.26 (d, J=8.6 Hz, 2H), 7.49 (d, J=8.1 Hz, 2H), 7.96 (d,
1
powder; m.p. 158.08C; H NMR: d=1.29 (d, J=7.0 Hz, 3H), 1.57 (s,
13
J=8.6 Hz, 2H); C NMR: d=21.4, 24.8, 27.9, 32.5, 42.7, 56.4, 58.8, 123.0,
3
1
7
1
1
1
H), 2.31 (s, 3H), 3.89 (dq, J=4.6, 7.0 Hz, 1H), 4.71 (dd, J=4.6, 8.8 Hz,
H), 6.42 (d, J=8.8 Hz, 1H), 7.02–7.08 (m, 7H), 7.32–7.38 (m, 2H),
1
2
1
23.1, 126.8, 126.9, 128.0, 128.1, 129.2, 129.3, 137.4, 143.9, 147.1, 147.2,
12.2; IR (KBr): n˜ = 3286, 2932, 2863, 1708, 1601, 1522, 1347, 1317,
1
3
.45–7.53 (m, 3H), 7.65–7.69 (m, 2H); C NMR: d=16.8, 21.5, 46.0, 60.7,
À1
152 cm
.
26.5, 126.8, 127.0, 128.1, 128.1, 128.5, 129.0, 133.3, 136.1, 137.8, 139.3,
2
-[1-(4-Methylphenyl)-1-tosylaminomethyl]cyclohexanone
(anti-3hg):
42.5, 203.6; IR (neat): n˜
=
3254, 3061, 2967, 1683, 1446, 1324,
1
White powder; m.p. 128.08C; H NMR: d=1.59–2.34 (m, 14H), 2.72 (dt,
J=5.4, 10.8 Hz, 1H), 4.38 (dd, J=5.4, 7.8 Hz, 1H), 6.03 (d, J=7.8 Hz,
1H), 6.88–6.96 (m, 4H), 7.05 (d, J=7.8 Hz, 2H), 7.47 (d, J=8.4 Hz, 2H);
À1
153 cm
.
Methyl-1,3-diphenyl-3-(tosylamino)propan-1-one
powder; m.p. 136.08C; H NMR: d=1.29 (d, J=7.0 Hz, 3H), 1.57 (s,
(syn-3ae):
White
1
13
C NMR: d=21.1, 21.4, 24.5, 28.0, 32.3, 42.6, 55.7, 58.9, 126.9, 127.1,
3
1
7
1
1
H), 2.31 (s, 3H), 3.89 (dq, J=4.6, 7.0 Hz, 1H), 4.71 (dd, J=4.6, 8.8 Hz,
H), 6.42 (d, J=8.8 Hz, 1H), 7.02–7.08(m, 7H), 7.32–7.38 (m, 2H), 7.45–
.53 (m, 3H), 7.65–7.69 (m, 2H); C NMR: d=14.7, 21.5, 46.7, 59.7,
128.5, 128.7, 128.8, 129.0, 135.9, 136.7, 137.4, 142.6, 212.5; IR (KBr): n˜ =
À1
A
H
R
U
G
3358, 3201, 2942, 2864, 1707, 1338, 1156 cm
.
1
3
2
-[1-(4-Methoxyphenyl)-1-tosylaminomethyl]cyclohexanone (anti-3dg):
1
26.9, 127.0, 127.1, 127.9, 128.0, 128.4, 129.1, 133.0, 135.7, 136.8, 139.4,
White powder; m.p. 129.08C; H NMR: d=1.59–2.42 (m, 11H), 2.72 (dt,
J=5.4, 10.8 Hz, 1H), 3.72 (s, 3H), 4.41 (dd, J=5.2, 7.6 Hz, 1H), 6.20 (d,
J=7.6 Hz, 1H), 6.60 (d, J=8.4 Hz, 2H), 6.98 (d, J=8.4 Hz, 2H), 7.05 (d,
À1
42.8, 201.4; IR (neat): n˜ = 3335, 2969, 1674, 1326, 1157 cm ; HRMS:
À
m/z: calcd for C23
H22NO
3
S: 392.1320; found: 392.1357[ MÀH] .
1
3
2
3
1
8
2
-Methyl-3-(4-nitrophenyl)-1-phenyl-3-tosylaminopropan-1-one
(anti-
J=8.4 Hz, 2H), 7.47 (d, J=8.4 Hz, 2H); C NMR: d=21.4, 24.1, 27.9,
1
ce): White powder; m.p. 133.08C; H NMR: d=1.35 (d, J=7.0 Hz, 3H),
.57(s, 3H), 3.91 (m, 1H), 4.80 (dd, J=4.1, 8.6 Hz, 1H), 6.68 (d, J=
.6 Hz, 1H), 7.11 (d, J=8.1 Hz, 2H), 7.25–7.28 (m, 2H), 7.34–7.40 (m,
H), 7.50–7.57 (m, 3H), 7.68 (d, J=7.3 Hz, 2H), 7.93 (d, J=8.6 Hz, 2H);
C NMR: d=17.0, 21.5, 45.6, 60.1, 123.3, 126.7, 127.5, 128.1, 128.7, 129.3,
31.4, 42.2, 55.1, 56.7, 58.4, 113.2, 126.2, 126.8, 128.2, 128.9, 129.4, 130.7,
À1
1
37.3, 142.4, 158.3, 212.6; IR (KBr): n˜ = 3300, 1710, 1605, 1149 cm
.
2-(trans-3-Phenyl-1-tosylaminopropan-2-en)cyclohexanone
(anti-3ig):
1
White powder; m.p. 170.08C; H NMR: d=1.62–2.40 (m, 12H), 2.56–2.62
(m, 1H), 3.89 (ddd, J=3.3, 7.6, 9.4 Hz, 1H), 5.54 (d, J=9.4 Hz, 1H),
5.87–6.03 (m, 2H), 6.98–7.01 (m, 2H), 7.10–7.26 (m, 5H), 7.47 (d, J=
1
3
1
2
4
34.0, 135.3, 137.6, 143.3, 146.7, 147.0, 202.9; IR (KBr): n˜ =3421, 3004,
361, 1714, 1360, 1223 cm
À1
13
;
HRMS: m/z: calcd for
C
23
H
21
N
2
O
5
S:
8.4 Hz, 2H); C NMR: d=21.4, 25.0, 27.8, 31.8, 42.9, 56.0, 58.2, 126.2,
+
37.1171; found: 437.1187 [M] .
127.2, 127.3, 127.6, 128.2, 129.3, 131.8, 135.9, 137.8, 143.1, 212.4; IR
À1
(
KBr): n˜ = 3298, 2936, 1694, 1596, 1494, 1449, 1160 cm
.
2
-Methyl-1-phenyl-1-(tosylamino)pentan-3-one
(anti-3af):
White
1
2-[1-(Pyridin-4-yl)-1-tosylaminomethyl]cyclohexanone (anti-3 fg): White
powder; m.p. 125.08C; H NMR: d=0.85 (t, J=7.3 Hz, 3H), 1.06 (d, J=
1
powder; m.p. 195.08C; H NMR: d=1.60–2.41 (m, 11H), 2.76–2.84 (m,
7
1
6
.0 Hz, 3H), 2.02 (dq, J=7.3, 18.9 Hz, 1H), 2.30 (s, 3H), 2.39 (dq, J=7.3,
8.9 Hz, 1H), 2.96 (dq, J=5.9, 7.0 Hz, 1H), 4.50 (dd, J=5.9, 8.9 Hz, 1H),
1
5
H), 4.43 (dd, J=3.8, 9.2 Hz, 1H), 6.27(d, J=9.2 Hz, 1H), 7.01 (d, J=
.7Hz, 2H), 7. 11 (d, J=8.4 Hz, 2H), 7.52 (d, J=8.4 Hz, 2H), 8.33 (d, J=
.32 (d, J=8.9 Hz, 1H), 6.96–7.11(m, 7H), 7.46 (d, J=8.4 Hz, 2H);
A
T
E
G
1
3
1
3
5.7Hz, 2H); C NMR: d=21.5, 24.8, 27.9, 32.7, 42.7, 56.3, 58.2, 122.0,
C NMR: d=7.19, 15.5, 21.4, 36.1, 51.1, 60.4, 126.3, 126.7, 127.1, 128.1,
1
26.7, 129.2, 137.4, 143.3, 148.4, 149.2, 211.6; IR (KBr): n˜ = 3037, 2947,
1
28.9, 137.6, 139. 1, 142.5, 214.9; IR (neat): n˜ = 3276, 3059, 2976, 2935,
À1
À1
2854, 1713, 1601, 1420, 1326, 1152 cm
C H O N S: 359.1429; found: 359.1437[ M+H] .
19 23 3 2
;
HRMS: m/z: calcd for
1
699, 1451,1326, 1160 cm
.
+
2
-Methyl-1-phenyl-1-(tosylamino)pentan-3-one (syn-3af): White powder;
1
m.p. 135.08C; H NMR: d=0.78 (t, J=7.3 Hz, 3H), 1.13 (d, J=7.0 Hz,
3
H), 2.00 (dq, J=7.3, 18.9 Hz, 1H), 2.23 (dq, J=7.3, 18.9 Hz, 1H), 2.33
(
s, 3H), 2.91 (dq, J=7.0, 7.6 Hz, 1H), 4.43 (dd, J=7.6, 8.0 Hz, 1H), 5.31
d, J=8.0 Hz, 1H), 6.91–7.12 (m, 7H), 7.48 (d, J=8.1 Hz, 2H);
C NMR: d=7.16, 13.6, 21.4, 35.7, 51.5, 59.6, 126.8, 126.9, 127.3, 128.1,
Acknowledgements
(
1
3
This study was supported in part by the Grant of the 21st Century COE
Program, Ministry of Education, Culture, Sports, Science and Technology
1
1
3
29.0, 136.8, 138.5, 142.8, 212.5; IR (KBr): n˜ = 3275, 2982, 1707, 1449,
À1
332, 1159 cm ; HRMS: m/z: calcd for C19
H
22NO
3
S: 344.1320; found:
(
MEXT).
À
44.1355 [MÀH] .
-(1-Phenyl-1-tosylaminomethyl)cyclohexanone
2
(anti-3ag): White
1
powder; m.p. 146.08C; H NMR: d=1.55–2.01 (m, 6H), 2.22–2.30 (m,
5
J=8.4 Hz, 1H), 7.00–7.08 (m, 7H), 7.44 (d, J=8.4 Hz, 2H); C NMR:
d=21.4, 24.4, 28.0, 32.2, 42.5, 56.7, 59.1, 126.8, 126.9, 127.0, 127.9, 128.9,
1
[1] a) I. Ojima, S. Inaba, K. Yoshida, Tetrahedron Lett. 1977, 3643; b) I.
Ojima, S. Inaba, M. Nagai, Synthesis 1981, 545.
[2] a) C. Gennari, I. Venturini, G. Gislon, G. Schimperna, Tetrahedron
Lett. 1987, 28, 227; b) G. Guanti, E. Narisano, L. Banfi, Tetrahedron
Lett. 1987, 28, 4331; c) E. W. Colvin, D. G. McGarry, J. Chem. Soc.
Chem. Commun. 1985, 539; d) T. Mukaiyama, K. Kashiwagi, S.
H), 2.74 (dt, J=5.1, 10.5 Hz, 1H), 4.43 (dd, J=5.1, 8.4 Hz, 1H), 6.15 (d,
1
3
37.4, 138.8, 142.6, 212.4; IR (neat): n˜
=
3282, 2940, 1710, 1446,
À1
1
157cm
.
5092
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 5082 – 5093