1774
A. Murali et al.
PAPER
1H NMR (400 MHz, CDCl3): d = 7.74 (d, J = 8.1 Hz, 2 H), 7.24 (d,
J = 8.1 Hz, 2 H), 6.52 (d, J = 7.4 Hz, 1 H), 4.15–4.13 (m, 1 H),
3.99–3.91 (m, 1 H), 2.41 (s, 3 H), 2.32 (s, 3 H), 2.08–1.95 (m, 4 H),
1.77–1.49 (m, 6 H), 1.48–1.43 (m, 2 H).
1H NMR (400 MHz, CDCl3): d (mixture of tautomers) = 7.76–7.70
(m, 2 H), 7.21–7.19 (m, 2 H), 6.30 (br s, 1 H), 5.31 (d, J = 7.2 Hz,
1 H), 4.81 (d, J = 7.6 Hz, 0.5 H), 4.17 (br s, 1 H), 3.93–3.83 (m, 3
H), 3.52 (t, J = 11.6 Hz, 2 H), 2.33 (s, 6 H), 2.11–1.94 (m, 6 H).
13C NMR (100 MHz, CDCl3): d = 164.5, 142.3, 140.7, 129.2, 126.2,
62.5, 51.7, 34.1, 32.3, 29.5, 27.7, 23.3, 22.9, 21.4, 21.1.
13C NMR (100 MHz, CDCl3): d = 165.4, 142.5, 139.9, 129.3, 126.5,
79.0, 67.6, 60.4, 58.3, 30.7, 21.5, 21.0, 19.1, 14.2.
HRMS (ESI): m/z [M]+ calcd for C17H25ClN2O2S: 357.1404; found:
HRMS (ESI): m/z [M + H]+ calcd for C14H20ClN2O3S: 331.0883;
357.1415.
found: 331.0883.
N-(2-Chlorocyclooctyl)-4-methylbenzenesulfonamide (1c)
Yield: 28 mg (9%); Rf = 0.6 (EtOAc–hexanes, 3:7).
N-(trans-3-Chlorotetrahydro-2H-pyran-2-yl)-N¢-tosylacetimi-
damide (trans-4b)
Rf = 0.4 (EtOAc–hexanes, 4:6).
IR (KBr): 3434, 3256, 3064, 3040, 2925, 2870, 1469, 1448, 1321,
1157, 1095 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.76 (d, J = 7.8 Hz, 2 H), 7.29 (d,
J = 7.6 Hz, 2 H), 4.93 (s, 1 H), 3.96–3.92 (m, 1 H), 3.33 (s, 1 H),
2.44 (s, 3 H), 2.13–1.34 (m, 12 H).
13C NMR (100 MHz, CDCl3): d = 143.4, 136.9, 129.5, 127.5, 65.6,
60.5, 32.0, 31.2, 25.7, 25.4, 25.3, 23.9, 21.5.
IR (neat): 3298, 2927, 2857, 1586, 1534, 1438, 1374, 1274, 1144,
1081, 1039, 932, 896, 810, 762, 698, 670 cm–1.
1H NMR (400 MHz, CDCl3): d (mixture of tautomers) = 7.83–7.80
(m, 2 H), 7.28–7.25 (m, 2 H), 5.85 (d, J = 7.2 Hz, 1 H), 5.19 (t,
J = 6.8 Hz, 0.4 H), 4.53 (dd, J = 8.1, 8.4 Hz, 0.6 H), 4.02–3.92 (m,
1 H), 3.76–3.74 (m, 1 H), 3.62–3.51 (m, 2 H), 2.42 (s, 3 H), 2.40 (s,
3 H), 1.89–1.69 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 166.9, 143.2, 142.3, 140.1, 136.8,
129.3, 129.1, 126.5, 126.3, 85.9, 82.6, 67.1, 66.7, 56.9, 56.7, 33.8,
33.6, 26.1, 25.6, 21.4, 20.9.
HRMS (ESI): m/z [M + H]+ calcd for C15H23ClNO2S: 316.1138;
found: 316.1135.
N-(2-Chlorocyclohexyl)-N¢-tosylacetimidamide (2b)
Yield: 1.07 g [89%, based on chloramine-T; Reaction conditions:
olefin/TfOH/chloramine-T = 2.0:2.0:1.0 (molar ratio), MeCN (4
mL/mmol of CT), r.t., 2 h]; Rf = 0.3 (EtOAc–hexanes, 3:7).
HRMS (ESI): m/z [M + H]+ calcd for C14H20ClN2O3S: 331.0883;
found: 331.0882.
N-[4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-chlorotetrahy-
dro-2H-pyran-2-yl]-N¢-tosylacetimidamide (cis-5b)
Yield (cis-5b + trans-5b): 102 mg (55%); Rf = 0.4 (EtOAc–hex-
anes, 1:1).
IR (neat): 3288, 3123, 2942, 2868, 1549, 1440, 1303, 1270, 1139,
1087, 810, 754, 700, 667 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.75 (d, J = 8.0 Hz, 2 H), 7.23 (d,
J = 8.0 Hz, 2 H), 6.99 (d, J = 8.4 Hz, 1 H), 4.09–4.01 (m, 1 H), 3.77
(dt, J = 10.4, 4.4 Hz, 1 H), 2.38 (s, 3 H), 2.26 (s, 3 H), 2.19–2.03 (m,
2 H), 1.72–1.62 (m, 3 H), 1.33–1.20 (m, 3 H).
IR (neat): 3299, 2922, 1592, 1534, 1450, 1271, 1143, 1063, 911,
809, 736, 694, 546 cm–1.
1H NMR (400 MHz, CDCl3): d (mixture of tautomers) = 7.76 (d,
J = 8.0 Hz, 0.4 H), 7.71 (d, J = 8.4 Hz, 1.3 H), 7.28–7.02 (m, 17 H),
5.97 (d, J = 8.8 Hz, 0.7 H), 5.26 (t, J = 8.4 Hz, 0.7 H), 4.91–4.84 (m,
1.2 H), 4.78–4.67 (m, 2.4 H), 4.56 (t, J = 8.4 Hz, 0.8 H), 4.51–4.44
(m, 2 H), 4.41–4.35 (m, 2.2 H), 3.79–3.70 (m, 0.8 H), 3.63–3.53 (m,
5.8 H), 3.49–3.41 (m, 1.3 H), 2.34 (s, 3 H), 2.32 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 166.9, 165.9, 143.3, 143.2, 142.4,
142.3, 140.0, 139.9, 137.7, 137.6, 137.2, 137.1, 129.8, 129.6, 129.4,
128.4, 128.4, 128.4, 128.3, 128.3, 128.0, 128.0, 127.9, 127.9, 127.9,
127.8, 127.8, 127.7, 127.6, 126.8, 126.6, 126.5, 126.3, 126.3, 80.7,
79.8, 78.5, 78.0, 76.5, 76.2, 75.0, 74.9, 73.9, 73.6, 73.5, 73.4, 73.4,
72.1, 68.4, 67.7, 57.6, 56.9, 21.4, 21.4, 21.3, 20.8.
13C NMR (100 MHz, CDCl3): d = 166.2, 142.2, 140.6, 129.2, 126.3,
61.4, 56.9, 35.9, 31.5, 25.2, 24.1, 21.5, 20.9.
HRMS (ESI): m/z [M + H]+ calcd for C15H22ClN2O2S: 329.1091;
found: 329.1090.
N-(2-Chlorocyclopentyl)-N¢-tosylacetimidamide (3b)
Yield: 1.1 g [95%, based on chloramine-T; Reaction conditions:
olefin/TfOH/chloramine-T = 2.0:2.0:1.0 (molar ratio), MeCN (4
mL/mmol of CT), r.t., 2 h]; Rf = 0.3 (EtOAc–hexanes, 3:7).
IR (neat): 2971, 1541, 1494, 1417, 1382, 1266, 1190, 1175, 1144,
1089, 1040, 906, 813, 724, 656 cm–1.
1H NMR (400 MHz, CDCl3): d (mixture of tautomers) = 8.07 (d,
J = 6.0 Hz, 0.8 H), 7.74 (dd, J = 6.8, 6.0 Hz, 3.7 H), 7.40 (d, J = 7.6
Hz, 2 H), 7.20 (d, J = 7.6 Hz, 1.9 H), 4.72 (d, J = 8.0 Hz, 1 H), 4.55
(d, J = 7.2 Hz, 1 H), 4.35–4.28 (m, 0.8 H), 4.23–4.18 (m, 0.8 H),
2.56 (s, 3 H), 2.44 (s, 3 H), 2.35 (s, 3 H), 2.30 (d, J = 0.8 Hz, 2.4 H),
2.27–2.04 (m, 5 H), 1.97–1.72 (m, 7 H), 1.60–1.44 (m, 2.6 H).
HRMS (ESI): m/z [M + H]+ calcd for C36H40ClN2O6S: 663.2296;
found: 663.2302.
N-[4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-chlorotetrahy-
dro-2H-pyran-2-yl]-N¢-tosylacetimidamide (trans-5b)
Rf = 0.3 (EtOAc–hexanes, 5:5).
13C NMR (100 MHz, CDCl3): d = 166.2, 165.4, 147.2, 141.9, 140.7,
133.9, 130.9, 129.1, 127.6, 126.2, 67.3, 64.1, 62.7, 61.2, 35.0, 34.2,
32.9, 29.0, 22.3, 21.8, 21.4, 21.2, 20.6, 14.9.
HRMS (ESI): m/z [M + H]+ calcd for C14H20ClN2O2S: 315.0934;
found: 315.0933.
IR (neat): 3296, 3035, 2869, 1592, 1535, 1449, 1275, 1214, 1144,
1062, 910, 809, 735, 694 cm–1.
1H NMR (400 MHz, CDCl3): d (mixture of tautomers) = 7.72–7.65
(m, 2 H), 7.33–7.11 (m, 17 H), 6.45 (d, J = 7.6 Hz, 0.4 H), 5.54 (t,
J = 6.8 Hz, 0.6 H), 5.20 (dd, J = 7.6, 4.0 Hz, 0.6 H), 4.76–4.36 (m,
6 H), 4.29 (dd, J = 6.4, 3.2 Hz, 0.7 H), 4.07 (t, J = 4.4 Hz, 0.5 H),
3.92–3.80 (m, 2 H), 3.70–3.59 (m, 2 H), 3.54–3.51 (m, 0.6 H), 3.42
(t, J = 5.2 Hz, 0.8 H), 2.34 (s, 3 H), 2.32 (s, 3 H).
N-(cis-3-Chlorotetrahydro-2H-pyran-2-yl)-N¢-tosylacetimid-
amide (cis-4b)
Yield (cis-4b + trans-4b): 1.2 g (73%); Rf = 0.5 (EtOAc–hexanes,
4:6).
HRMS (ESI): m/z [M + Na]+ calcd for C36H39ClN2O6SNa:
685.2115; found: 685.2103.
IR (neat): 3298, 2927, 2857, 1586, 1534, 1438, 1374, 1274, 1144,
1081, 1039, 932, 896, 810, 762, 698, 670 cm–1.
Synthesis 2011, No. 11, 1771–1776 © Thieme Stuttgart · New York