6
Y. Hu et al. / Tetrahedron xxx (2015) 1e9
1
3
1
1
29.0, 128.3, 78.6, 73.3, 37.9, 21.8, 21.7; HRMS (ESI-TOF) m/z calcd
J¼2.4 Hz, 1H); C{ H} NMR (100 MHz, CDCl
3
) d 164.6, 136.4, 132.9,
þ
for C18
H18NO
3
S [MþH] 328.1002, found 328.1008.
131.5, 130.2, 128.5, 122.7, 77.5, 75.5, 52.9; HRMS (ESI-TOF) m/z calcd
for C10H
8
BrO
2
[MþH]þ 238.9702, found 238.9712.
4
.2.2.4. N-(Prop-2-yn-1-yl)-N-tosyl-4-(trifluoromethyl)benza-
mide (3d). By following the general procedure (2.0 mmol), the
compound was obtained as a white solid (488.1 mg), 64% yield, mp
4.2.2.11. Prop-2-yn-1-yl 4-methoxybenzoate (3m). By following
17
the reported procedure (10.0 mmol), the compound was obtained
ꢁ
1
1
1
(
(
10e111 C; H NMR (400 MHz, CDCl
3
)
d
7.81 (d, J¼8.2 Hz, 2H), 7.62
as yellow oil (283.2 mg), 18% yield; H NMR (400 MHz, CDCl
3
)
q, J¼8.3 Hz, 4H), 7.30 (d, J¼8.1 Hz, 2H), 4.59 (d, J¼2.2 Hz, 2H), 2.44
d
8.14e7.92 (m, 2H), 6.98e6.87 (m, 2H), 4.89 (d, J¼2.4 Hz, 2H), 3.85
13
1
13
1
s, 3H), 2.37 (t, J¼2.1 Hz, 1H); C{ H} NMR (100 MHz, CDCl
3
)
(s, 3H), 2.52 (t, J¼2.5 Hz, 1H); C{ H} NMR (100 MHz, CDCl
3
)
d
169.3, 145.6, 137.6, 135.3, 133.3 (q, J¼32.9 Hz), 129.7, 128.8, 128.3,
d 165.5, 163.7, 131.9, 121.8, 113.8, 78.1, 74.9, 55.5, 52.2; HRMS (ESI-
1
25.4 (q, J¼3.7 Hz), 123.6 (q, J¼272.6 Hz), 78.2, 73.5, 37.3, 21.8;
TOF) m/z calcd for C11
H
11
O
3
[MþH]þ 191.0703, found 191.0710.
HRMS (ESI-TOF) m/z calcd for C18
H
15
F
3
NO
3
S [MþH]þ 382.0719,
found 382.0724.
4.3. Representative procedure for the ring-closure/opening
cascade reactions of allylamides
4.2.2.5. 4-Fluoro-N-(prop-2-yn-1-yl)-N-tosylbenzamide (3e). By
following the general procedure (4.0 mmol), the compound was
In a 10 mL flame-dried Schlenk flask, allylamide 1 (0.20 mmol)
and NIS (1.2 equiv) were dissolved in 3 mL of dry dichloromethane
ꢁ
1
obtained as a white solid (657.7 mg), 50% yield, mp 87e88 C; H
NMR (400 MHz, CDCl
7.84 (d, J¼8.4 Hz, 2H), 7.64e7.50 (m, 2H),
.31 (d, J¼8.1 Hz, 2H), 7.18e6.97 (m, 2H), 4.56 (d, J¼2.4 Hz, 2H), 2.44
3
)
d
and then H
stirred at room temperature for 12 h, and quenched with sodium
thiosulfate solution. The aqueous layer was extracted with Et O and
the combined organic layers were washed twice with brine, dried
over MgSO , filtered, and concentrated under reduced pressure.
2
O (2.0 equiv) was added. The resulting solution was
7
1
3
1
(
d
s, 3H), 2.35 (t, J¼2.4 Hz, 1H); C{ H} NMR (100 MHz, CDCl
3
)
2
169.7, 164.9 (d, J¼253.7 Hz), 145.4, 135.5,130.9 (d, J¼9.0 Hz), 129.6,
1
28.9, 128.6, 115.7 (d, J¼22.1 Hz), 78.4, 73.4, 37.7, 21.8; HRMS (ESI-
4
þ
TOF) m/z calcd for C17
H15FNO
3
S [MþH] 332.0751, found 332.0750.
Purification by flash chromatography on silica gel (petroleum
ether/EtOAc: 5:1) afforded the expected product.
4
.2.2.6. 4-Methoxy-N-(prop-2-yn-1-yl)-N-tosylbenzamide
3f). By following the general procedure (2.0 mmol), the com-
pound was obtained as a white solid (336.8 mg), 51% yield, mp
(
4.3.1. 1-Iodo-3-(4-methylphenylsulfonamido)propan-2-yl benzoate
(2a). By following the representative procedure (0.2 mmol), the
title compound was obtained as a white solid (91.0 mg), 98% yield,
ꢁ
1
9
6e97 C; H NMR (400 MHz, CDCl
3
)
d
7.88 (d, J¼8.3 Hz, 2H), 7.62
ꢁ
1
(
(
d, J¼8.7 Hz, 2H), 7.30 (d, J¼8.1 Hz, 2H), 6.89 (d, J¼8.7 Hz, 2H), 4.54
mp 91e92 C; H NMR (400 MHz, acetone) d 8.12e7.91 (m, 2H),
1
3
d, J¼2.2 Hz, 2H), 3.85 (s, 3H), 2.43 (s, 3H), 2.33 (t, J¼2.2 Hz, 1H);
C
7.79e7.71 (m, 2H), 7.70e7.59 (m, 1H), 7.57e7.45 (m, 2H), 7.35 (d,
J¼8.1 Hz, 2H), 6.89 (t, J¼6.5 Hz, 1H), 5.62e4.84 (m, 1H), 3.78e3.45
1
{
3
H} NMR (100 MHz, CDCl ) d 170.4, 163.0, 145.0, 135.6, 130.9, 129.5,
13
1
1
28.9, 126.1, 113.8, 78.6, 73.3, 55.6, 38.0, 21.8; HRMS (ESI-TOF) m/z
(m, 2H), 3.51e3.31 (m, 2H), 2.38 (s, 3H); C{ H} NMR (100 MHz,
calcd for C18
H18NO
4
S [MþH]þ 344.0951, found 344.0949.
acetone) d 165.8, 144.0, 138.8, 134.1, 130.6, 130.49, 130.47, 129.3,
1
C
28.0, 72.9, 46.5, 21.4, 5.2; HRMS (ESI-TOF) m/z calcd for
4.2.2.7. N-(Prop-2-yn-1-yl)-N-tosylacetamide (3g). By following
17
H19INO
4
S [MþH]þ 460.0074, found 460.0082.
the general procedure (3.0 mmol), the compound was obtained as
1
colorless oil (109.4 mg), 19% yield; H NMR (400 MHz, CDCl
3
)
d
7.91
4.3.2. 1-Iodo-3-(4-methylphenylsulfonamido)propan-2-yl 3-
bromobenzoate (2b). By following the representative procedure
(0.2 mmol), the title compound was obtained as a yellow solid
(
(
d, J¼8.4 Hz, 2H), 7.35 (d, J¼8.0 Hz, 2H), 4.67 (d, J¼2.4 Hz, 2H), 2.45
13
1
3
s, 3H), 2.35e2.28 (m, 4H); C{ H} NMR (100 MHz, CDCl ) d 169.5,
ꢁ
1
1
45.3,136.0,129.9,128.1, 78.4, 72.6, 35.5, 24.5, 21.7; HRMS (ESI-TOF)
(94.4 mg), 88% yield, mp 94e95 C; H NMR (400 MHz, acetone)
m/z calcd for C12
H14NO
3
S [MþH]þ 252.0689, found 252.0689.
d
8.13 (t, J¼1.8 Hz,1H), 8.00 (dt, J¼7.8, 1.3 Hz, 1H), 7.87e7.79 (m, 1H),
.78e7.69 (m, 2H), 7.49 (t, J¼7.9 Hz, 1H), 7.34 (d, J¼8.0 Hz, 2H), 6.89
7
4
.2.2.8. N-(Prop-2-yn-1-yl)-N-tosylfuran-2-carboxamide
(t, J¼6.5 Hz, 1H), 5.10 (p, J¼5.4 Hz, 1H), 3.73e3.49 (m, 2H),
13 1
(
3h). By following the general procedure (4.0 mmol), the com-
3.48e3.26 (m, 2H), 2.38 (s, 3H); C{ H} NMR (100 MHz, Acetone)
d 164.5, 144.0, 138.8, 137.0, 133.1, 132.8, 131.4, 130.4, 129.4, 127.6,
1
pound was obtained as yellow oil (157.7 mg), 13% yield; H NMR
400 MHz, CDCl
(
3
2
3
)
d
8.00 (d, J¼8.3 Hz, 2H), 7.57 (s, 1H), 7.44e7.29 (m,
122.8, 73.5, 46.4, 21.4, 4.7; HRMS (ESI-TOF) m/z calcd for
H), 6.53 (dd, J¼3.5, 1.6 Hz, 1H), 4.93 (d, J¼2.3 Hz, 2H), 2.43 (s, 3H),
C
17
H
18IBrNO
4
S [MþH]þ 537.9179, found 537.9180.
13
1
.32 (t, J¼2.3 Hz, 1H); C{ H} NMR (100 MHz, CDCl
3
) d 158.4, 146.4,
1
46.0, 145.1, 135.9, 129.5, 129.1, 120.6, 112.4, 78.6, 73.3, 36.8, 21.8;
4.3.3. 1-Iodo-3-(4-methylphenylsulfonamido)propan-2-yl 4-
methoxybenzoate (2c). By following the representative procedure
þ
HRMS (ESI-TOF) m/z calcd for C15
04.0636.
H14NO
4
S [MþH] 304.0638, found
3
(0.2 mmol), the title compound was obtained as colorless oil
1
(
110.7 mg), 93% yield; H NMR (400 MHz, acetone)
d
8.05e7.88 (m,
4
.2.2.9. N-Benzyl-N-(prop-2-yn-1-yl)benzamide (3j). By follow-
2H), 7.82e7.67 (m, 2H), 7.49e7.25 (m, 2H), 7.12e6.95 (m, 2H), 6.87
(t, J¼6.5 Hz, 1H), 5.02 (p, J¼5.4 Hz, 1H), 3.89 (s, 3H), 3.74e3.48 (m,
16
ing the reported procedure (4.0 mmol), the compound was ob-
ꢁ
1
13
1
tained as a white solid (475.2 mg), 50% yield, mp 48e49 C; H NMR
400 MHz, CDCl 7.77e7.16 (m, 10H), 4.73 (br, 2H), 4.02 (br, 2H),
.76e1.85 (m, 1H); C{ H} NMR (100 MHz, CDCl
35.1,129.7,128.5,128.2,127.4,126.9,126.6, 78.2, 72.8 (br), 49.3 (br),
5.4 (br); HRMS (ESI-TOF) m/z calcd for C17
2H), 3.37 (dd, J¼6.5, 5.5 Hz, 2H), 2.39 (s, 3H); C{ H} NMR
(
2
1
3
3
)
d
(100 MHz, acetone) d 165.5, 164.7, 144.0, 138.8, 132.6, 130.5, 127.7,
13
1
3
)
d
170.9, 136.0,
122.8, 114.5, 72.4, 56.0, 46.5, 21.4, 5.4; HRMS (ESI-TOF) m/z calcd for
C
18
H21INO
5
S [MþH]þ 490.0180, found 490.0180.
H
16NO [MþH]þ
2
50.1226, found 250.1244.
4.3.4. 1-Iodo-3-(4-methylphenylsulfonamido)propan-2-yl 4-
fluorobenzoate (2d). By following the representative procedure
(0.2 mmol), the title compound was obtained as a yellow solid
4
.2.2.10. Prop-2-yn-1-yl 3-bromobenzoate (3l). By following the
17
ꢁ
1
reported procedure (10.0 mmol), the compound was obtained as
(83.8 mg), 88% yield, mp 96e97 C; H NMR (400 MHz, acetone)
8.33e7.95 (m, 2H), 7.91e7.68 (m, 2H), 7.40e7.32 (m, 2H),
7.32e7.22 (m, 2H), 6.90 (t, J¼6.5 Hz, 1H), 5.07 (p, J¼5.4 Hz, 1H),
1
yellow oil (798.4 mg), 35% yield; H NMR (400 MHz, CDCl
t, J¼1.8 Hz, 1H), 8.00 (dt, J¼7.9, 1.3 Hz, 1H), 7.71 (ddd, J¼8.0, 2.1,
.0 Hz, 1H), 7.33 (t, J¼7.9 Hz, 1H), 4.93 (d, J¼2.5 Hz, 2H), 2.53 (t,
3
)
d
8.20
d
(
1
13
1
3.82e3.47 (m, 2H), 3.40 (dd, J¼6.5, 5.5 Hz, 2H), 2.39 (s, 3H); C{ H}