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The Journal of Organic Chemistry
The product selectivity was measured after chromatog-
2-fluoro-N-(1-(pyridin-2-yl)-2-(tosylmethyl)allyl)ben-
zamide (4c) 1H NMR resonances distinguishable at: d 8.58,
6.09, 5.41, 5.23, 4.04, 3.73.
raphy using 1H NMR integration ratios of the purified frac-
tions. Run 1 (54 mg, 66%, 99:1); Run 2 (49.7 mg, 61%, 98:2).
1H NMR (400 MHz, CDCl3) d 8.88 (d, J = 8.5 Hz, 1 H), 8.57-
8.56 (m, 2 H), 8.15 (d, J = 7.8 Hz, 1 H), 7.85-7.79 (m, 3 H),
7.61 (dt, J = 7.6, 1.8 Hz, 1 H), 7.41 (ddd, J = 7.7, 4.8, 1.1 Hz, 1
H), 7.31 (d, J = 8.0 Hz, 2 H), 7.26-7.24 (m, 1 H), 7.18 (ddd, J =
7.7, 4.8, 0.9 Hz, 1 H), 6.32 (s, 1 H), 5.66 (s, 1 H), 5.54 (q, J =
7.4 Hz, 1 H), 2.99 (dd, J = 15.4, 7.5 Hz, 1 H), 2.88 (dd, J = 15.4,
7.2 Hz, 1 H), 2.42 (s, 3 H); 13C{1H} NMR (100 MHz, CDCl3) d
163.9, 158.6, 149.8, 148.4, 146.7, 144.7, 137.4, 136.8, 135.6,
130.0 (2 C), 128.7 (2 C), 126.4, 126.2, 122.9 (2 C), 122.4,
52.8, 35.9, 21.8; IR (cm−1) 3366, 2923, 1669, 1591, 1506,
1432, 1289, 1132, 1081, 731; HRMS (ESI) m/z: [M + H]+
Calcd for C22H22N3O3S 408.1376; Found 408.1390; mp 64-
75 °C; TLC Rf = 0.66 (100% ethyl acetate/hexane), visual-
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2-methoxy-N-(1-(pyridin-2-yl)-3-tosylbut-3-en-1-yl)ben-
zamide (3d). Follows general procedure D. 1d (49 mg, 0.2
mmol), 2a (78 mg, 0.4 mmol), THF (1 mL). The residue was
purified by silica gel flash chromatography (20-70% ethyl
acetate/hexane) to yield the title compound as a red-brown
solid. The product selectivity was measured after chroma-
tography using 1H NMR integration ratios. Run 1 (49.6 mg,
56%, 96:4; 2-picolyl amide 1d recovered 7.3 mg; yield
based on recovered starting material 66%); Run 2 (45.9 mg,
52%, 97:3; 2-picolyl amide 1d recovered 10.1 mg; yield
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based on recovered starting material 65%). H NMR (400
MHz, CDCl3) d 8.84 (d, J = 7.5 Hz, 1 H), 8.55 (dd, J = 4.8, 0.8
Hz, 1 H), 8.14 (dd, J = 7.8, 1.8 Hz, 1 H), 7.79 (d, J = 8.3 Hz, 2
H), 7.61 (dt, J = 7.7, 1.8 Hz, 1 H), 7.44 (dt, J = 7.8, 1.8 Hz, 1 H),
7.31-7.26 (m, 3 H), 7.17 (ddd, J = 7.5, 4.9, 1.0 Hz, 1 H), 7.05
(dt, J = 7.7, 0.9 Hz, 1 H), 6.96 (d, J = 8.2 Hz, 1 H), 6.34 (s, 1 H),
5.70 (s, 1 H), 5.57 (q, J = 7.4 Hz, 1 H), 3.96 (s, 3 H), 3.02 (dd,
J = 15.5, 7.7 Hz, 1 H), 2.81 (dd, J = 15.5, 6.9 Hz, 1 H), 2.41 (s,
3 H); 13C{1H} NMR (100 MHz, CDCl3) d 164.9, 159.1, 157.9,
149.6, 147.0, 144.6, 136.8, 135.7, 133.0, 132.3, 130.0 (2 C),
128.7 (2 C), 125.9, 122.8, 122.7, 121.5, 121.3, 111.5, 56.1,
53.5, 35.6, 21.8; IR (cm−1) 3370, 2925, 1647, 1596, 1517,
1482, 1290, 1134, 1081, 731; HRMS (ESI) m/z: [M + H]+
Calcd for C24H25N2O4S 437.1530; Found 437.1517; mp 49-
56 °C; TLC Rf = 0.27 (100% ethyl acetate/hexane), visual-
ized with UV.
N-(1-(pyridin-2-yl)-2-(tosylmethyl)allyl)picolinamide (4f)
1H NMR resonances distinguishable at: d 6.08, 5.37, 5.20,
4.04, 3.75 ppm.
N-(1-(pyridin-2-yl)-3-tosylbut-3-en-1-yl)thiophene-2-car-
boxamide (3g). Follows general procedure C. 1g (43.7 mg,
0.2 mmol), 1-methyl-4-(propa-1,2-dien-1-ylsulfonyl)ben-
zene (78 mg, 0.4 mmol), THF (1 mL). The crude product was
purified by silica gel flash chromatography (20-70% ethyl
acetate/hexane) to yield the title compound as a light-
brown solid. The product selectivity was measured after
1
chromatography using H NMR integration ratios. Run 1
(47.7 mg, 58%, 94:6); Run 2 (46.1 mg, 56%, 94:6). H NMR
1
ized with UV.
2-methoxy-N-(1-(pyridin-2-yl)-2-(tosylmethyl)allyl)ben-
zamide (4d) 1H NMR resonances distinguishable at: d 6.10,
5.41.
(400 MHz, CDCl3) d 8.54 (d, J = 4.7 Hz, 1 H), 7.80 (d, J = 8.2
Hz, 2 H), 7.66-7.62 (m, 3 H), 7.48 (dd, J = 5.0, 0.9 Hz, 1 H),
7.34 (d, J = 8.2 Hz, 2 H), 7.29 (d, J = 7.8 Hz, 1 H), 7.19 (dd, J =
7.5, 5.3 Hz, 1 H), 7.08 (dd, J = 4.9, 3.8 Hz, 1 H), 6.33 (s, 1 H),
5.62 (s, 1 H), 5.46 (q, J = 7.4 Hz, 1 H), 2.98 (dd, J = 15.1, 7.8
Hz, 1 H), 2.77 (dd, J = 15.2, 6.3 Hz, 1 H), 2.43 (s, 3 H); 13C{1H}
NMR (100 MHz, CDCl3) d 161.6, 158.6, 149.5, 146.5, 145.0,
139.0, 137.0, 135.2, 130.5, 130.2 (2 C), 128.7 (2 C), 128.4,
127.8, 127.0, 122.9, 122.5, 54.1, 35.4, 21.8; IR (cm−1) 3344,
2923, 1635, 1592, 1533, 1508, 1438, 1289, 1136, 1081, 730;
HRMS (ESI) m/z: [M + H]+ Calcd for C21H21N2O3S2 413.0988;
Found 413.1008; mp 90-98 °C; TLC Rf = 0.19 (50% ethyl ac-
etate/hexane), visualized with UV.
N-(1-(pyridin-2-yl)-3-tosylbut-3-en-1-yl)-1-naphthamide
(3e). Follows general procedure C. 1e (52.5 mg, 0.2 mmol),
2a (78 mg, 0.4 mmol), THF (1 mL). The residue was purified
by silica gel flash chromatography (20-70% ethyl ace-
tate/hexane) to yield the title compound as a light-brown
solid. The product selectivity was measured after chroma-
tography using 1H NMR integration ratios. Run 1 (52.8 mg,
1
58%, 94:6); Run 2 (56.7 mg, 62%, 95:5). H NMR (400 MHz,
CDCl3) d 8.52 (d, J = 4.1 Hz, 1 H), 8.29-8.26 (m, 1 H), 7.92 (d,
J = 8.2 Hz, 1 H), 7.87-7.82 (m, 3 H), 7.67 (dt, J = 7.7, 1.7 Hz, 1
H), 7.62 (dd, J = 7.0, 1.0 Hz, 1 H), 7.54-7.49 (m, 2 H), 7.45 (dd,
J = 7.2, 8.2 Hz, 1 H), 7.34 (d, J = 7.8 Hz, 1 H), 7.31-7.29 (m, 3
H), 7.21 (ddd, J = 7.8, 4.8, 0.9 Hz, 1 H), 6.39 (s, 1 H), 5.72 (s,
1 H), 5.69 (q, J = 7.6 Hz, 1 H), 3.04 (dd, J = 15.2, 7.6 Hz, 1 H),
2.83 (dd, J = 15.3, 6.8 Hz, 1 H), 2.40 (s, 3 H); 13C{1H} NMR
(100 MHz, CDCl3) d 169.0, 158.4, 149.6, 146.8, 144.9, 136.9,
135.3, 134.1, 133.9, 131.0, 130.4, 130.1 (2 C), 128.8 (2 C),
128.4, 127.2, 126.5, 126.4, 125.6, 125.3, 124.9, 123.0, 122.9,
53.4, 36.2, 21.8; IR (cm−1) 3330, 2927, 1651, 1592, 1515,
1291, 1134, 1082, 782, 732; HRMS (ESI) m/z: [M + H]+ Calcd
for C27H25N2O3S 457.1580; Found 457.1602; mp 105-114 °
N-(1-(pyridin-2-yl)-2-(tosylmethyl)allyl)thiophene-2-car-
boxamide (4g) 1H NMR resonances distinguishable at:
d 8.58, 8.15, 5.98, 5.38, 4.09, 3.75.
N-(1-(pyridin-2-yl)-3-tosylbut-3-en-1-yl)acetamide (3h).
Follows general procedure C. 1h (30.0 mg, 0.2 mmol), 1-me-
thyl-4-(propa-1,2-dien-1-ylsulfonyl)benzene (78 mg, 0.4
mmol), THF (1 mL). The residue was purified by silica gel
flash chromatography (50-100% ethyl acetate/hexane then
10-40% acetone/ethyl acetate) to yield the title compound
as a red-brown solid. The product selectivity was measured
after chromatography using 1H NMR integration ratios. Run
1
1 (41.4 mg, 60%, 94:6); Run 2 (39.1 mg, 57%, 94:6). H NMR
C; TLC Rf = 0.26 (50% ethyl acetate/hexane), visualized with
UV.
(400 MHz, CDCl3) d 8.50 (d, J = 4.6 Hz, 1 H), 7.78 (d, J = 8.2
Hz, 2 H), 7.61 (dt, J = 7.7, 1.6 Hz, 1 H), 7.34 (d, J = 8.2 Hz, 2
H), 7.21-7.16 (m, 2 H), 6.80 (d, J = 7.0 Hz, 1 H), 6.30 (s, 1 H),
5.55 (s, 1 H), 5.31 (q, J = 7.4 Hz, 1 H), 2.85 (dd, J = 15.1, 7.4
Hz, 1 H), 2.65 (dd, J = 15.1, 6.9 Hz, 1 H), 2.43 (s, 3 H), 1.98 (s,
3 H); 13C{1H} NMR (100 MHz, CDCl3) d 169.8, 158.5, 149.5,
146.7, 144.9, 136.8, 135.3, 130.1 (2 C), 128.7 (2 C), 126.4,
122.9, 122.8, 53.2, 35.7, 23.4, 21.8; IR (cm−1) 3283, 3056,
1655, 1593, 1531, 1435, 1289, 1135, 1081, 728; HRMS (ESI)
N-(1-(pyridin-2-yl)-2-(tosylmethyl)allyl)-1-naphthamide
1
(4e) H NMR resonances distinguishable at: d 6.20, 5.38,
5.19, 4.16, 3.81 ppm.
N-(1-(pyridin-2-yl)-3-tosylbut-3-en-1-yl)picolinamide (3f).
Follows general procedure C. 1f (42.6 mg, 0.2 mmol), 2a (78
mg, 0.4 mmol), THF (1 mL). The crude product was purified
by silica gel flash chromatography (20-70% ethyl ace-
tate/hexane) to yield the title compound as an orange solid.
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