K.O. Jeon et al. / Tetrahedron 65 (2009) 4992–5000
4997
1H), 3.28 (dd, J¼12.2, 2.0 Hz, 1H), 2.78 (ddd, J¼13.9, 8.0, 5.7 Hz, 1H),
2H), 2.00 (ddd, J¼7.7, 14.1, 17.0 Hz, 1H); 13C NMR (125 MHz, CDCl3)
2.21 (ddd, J¼14.2,11.1, 7.3 Hz,1H); 13C NMR (125 MHz, CDCl3)
d
ppm
d ppm 178.8, 178.7, 178.4 (2), 137.3, 137.2, 136.3, 136.2, 134.4, 134.0,
135.9, 134.4, 132.8, 128.9, 128.3, 127.3, 126.7, 124.0, 87.5, 82.2, 71.3,
51.9, 51.0, 34.4; HRMS calculated for C16H17NNaO3S (MþNa)þ
326.0827, found 326.0795.
131.9 (2),129.1,129.0,128.6,128.5,126.4 (2),125.7,125.6,118.2,117.8,
116.6, 116.5, 86.0, 85.7, 82.2, 81.7, 66.7 (2), 57.9, 57.0, 49.5, 49.2, 39.4,
39.0, 38.9 (2), 34.9, 34.8, 25.6 (2), 24.3, 24.1; HRMS calculated for
C24H26N2NaO5S (MþNa)þ 477.1460, found 477.1436.
4.2.6. Sultam [(ꢁ) 9]
According to general procedure, 1 (80 mg, 0.3 mmol), cat-B
(30 mg, 0.03 mmol), and 4-bromostyrene (3.9 mL, 30 mmol) were
added to argon degassed, dry CH2Cl2 (85 mL, 0.005 M) to yield ( ) 9
[87 mg, 0.23 mmol, 80%] as a white solid. Mp 140 ꢀC; FTIR (neat):
4.2.10. Sultam [(ꢁ) 15]
To a flame dried flask under argon were added furfural (1.72 mL,
20.8 mmol), 4-methoxybenzylamine (2.7 mL, 20.8 mmol), MgSO4
(3.0 g), and dry CH2Cl2 (20 mL). After stirring at rt for 6 h, the crude
reaction mixture was filtered and the filtrate was concentrated
under reduced pressure. The crude was dissolved in THF (20 mL) to
which was added allyl magnesium bromide (5.57 mL, 11.15 mmol).
The reaction mixture was stirred for 5 h. after which time NH4Cl
(satd aq, 10 mL) was added. The aqueous layer was extracted with
CH2Cl2 (4ꢃ20 mL) and the combined organic layer was dried
(MgSO4). The crude reaction mixture 14 (1.2 g) was solvated in dry
toluene (5 mL) and heated at reflux for 12 h. After such time the
crude reaction mixture concentrated under reduced pressure and
purified by flash chromatography (1:1 hexane/EtOAc) to provide
the desired compound (95% yield) as a yellow liquid. FTIR (neat):
1612, 1514, 1301, 1247, 1137 cmꢂ1. [Mixture of diastereoisomers
1487, 1350, 1338, 1164, 744 cmꢂ1; 1H NMR (500 MHz, CDCl3)
d ppm
7.48–7.43 (m, 2H), 7.25 (dt, J¼9.0, 2.2 Hz, 2H), 6.58 (d, J¼15.8 Hz,
1H), 6.33 (dq, J¼10.1, 2.1 Hz, 1H), 6.14 (dd, J¼15.8, 6.9 Hz, 1H), 5.57
(dt, J¼10.1, 2.5 Hz, 1H), 4.99 (q, J¼7.1 Hz, 1H), 4.22 (dt, J¼19.5,
2.5 Hz, 1H), 3.84–3.73 (m, 2H), 3.65 (dd, J¼12.2, 2.0 Hz, 1H), 3.28
(dd, J¼12.2, 2.0 Hz,1H), 2.77 (ddd, J¼13.9, 8.0, 5.7 Hz,1H), 2.19 (ddd,
J¼114.2, 11.1, 7.4 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d ppm 134.8,
134.3,131.8,131.5,128.2, 128.1,124.1,122.1, 87.6, 81.9, 71.2, 51.9, 51.0,
34.3; HRMS calculated for C16H16BrNNaO3S (MþNa)þ 403.9932,
found 403.9619.
4.2.7. Sultam [(ꢁ) 10]
According to general procedure A, 1 (80 mg, 0.3 mmol), cat-B
(30 mg, 0.03 mmol), and acrylonitrile (1.9 mL, 30 mmol) was added
to argon degassed, dry CH2Cl2 (85 mL, 0.005 M) to yield ( ) 10
[50 mg, 0.20 mmol, 67%] as a white solid. Mp 170 ꢀC; FTIR (neat):
(1:1)] 1H NMR (500 MHz, CDCl3)
d
ppm 7.37 (d, J¼8.6 Hz, 1H), 7.32
(d, J¼8.6 Hz, 1H), 6.95–6.81 (m, 4H), 6.52 (dd, J¼5.8, 1.7 Hz, 1H),
6.47–6.38 (m, 3H), 6.18 (d, J¼5.7 Hz, 1H), 5.93–5.78 (m, 1H), 5.74–
5.58 (m, 1H), 5.28 (dd, J¼4.5, 1.5 Hz, 1H), 5.22–5.14 (m, 2H), 5.09–
4.97 (m, 2H), 4.51 (d, J¼15.7 Hz, 1H), 4.41 (d, J¼15.3 Hz, 1H), 4.28
(dd, J¼15.5, 8.7 Hz, 2H), 3.81 (dd, J¼8.9, 5.6 Hz, 6H), 3.72 (t,
J¼5.3 Hz, 1H), 3.24 (dd, J¼7.9, 3.2 Hz, 1H), 3.13 (dd, J¼7.8, 3.3 Hz,
1H), 2.74–2.59 (m,1H), 2.56–2.48 (m,1H), 2.45 (t, J¼7.2 Hz,1H),1.80
1338, 1164, 1114 cmꢂ1 1H NMR (500 MHz, CDCl3)
; d ppm 6.67 (dd,
J¼16.2, 4.3 Hz, 1H), 6.28 (dq, J¼10.1, 2.1 Hz, 1H), 5.67 (dd, J¼1.9,
16.2 Hz,1H), 5.60 (dt, J¼10.1, 2.5 Hz,1H), 5.03–4.96 (m,1H), 4.21 (dt,
J¼19.6, 2.5 Hz, 1H), 3.80 (dt, J¼19.6, 2.2 Hz, 1H), 3.72 (ddd, J¼10.8,
6.4,1.9 Hz,1H), 3.58 (dd, J¼2.0,12.3 Hz,1H), 3.29 (dd, J¼2.0,12.3 Hz,
1H), 2.86–2.79 (m, 1H), 2.16 (ddd, J¼14.1, 10.9, 6.9 Hz, 1H); 13C NMR
(td, J¼12.4, 7.9 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d ppm 159.3,
159.2,139.7,137.9,135.3,132.9,132.6,132.1,130.0,129.9,127.6,127.3,
119.4, 118.9, 114.1, 114.1, 94.5, 92.2, 79.4, 78.8, 60.4, 59.7, 58.6, 58.4,
55.3, 55.3, 46.6, 46.0, 34.6, 33.8, 30.1, 29.5; HRMS calculated for
C18H21NNaO4S (MþNa)þ 370.1089, found 370.1075.
(125 MHz, CDCl3)
d ppm 149.9, 132.3, 123.5, 115.4, 99.4, 87.1, 78.4,
69.1, 50.9, 49.9, 32.2; HRMS calculated for C11H12N2NaO3S (MþNa)þ
275.0466, found 275.0468.
4.2.8. Sultam [(ꢁ) 12]
4.2.11. Sultam [(ꢁ) 16]
According to general procedure A, 2 (80 mg, 0.3 mmol) and cat-
B (30 mg, 0.03 mmol) were added to argon degassed, dry CH2Cl2
(85 mL, 0.005 M) to yield ( ) 12 [63 mg, 0.23 mmol, 75%] as a brown
According to general procedure A, 15 (0.06 g, 0.17 mmol), cat-B
(0.015 g, 0.017 mmol) in ethylene degassed CH2Cl2 (35 mL) and the
crude reaction mixture were purified by flash chromatography (2:1
hexane/EtOAc) to provide 16 (32 mg, 54%) and 17 (10 mg, 16%). FTIR
liquid. FTIR (neat): 2927, 1597, 1311, 1150, 931 cmꢂ1 1H NMR
;
(500 MHz, CDCl3)
d
ppm 6.36 (dd, J¼17.7, 11.1 Hz, 1H), 5.99 (dd,
(neat): 1612, 1514, 1305, 1249, 1149 cmꢂ1
CDCl3) d ppm 7.42–7.22 (m, 2H), 7.11–6.74 (m, 2H), 6.10–5.87 (m,
;
1H NMR (500 MHz,
J¼17.0, 10.6 Hz, 1H), 5.81 (ddd, J¼17.2, 10.3, 6.9 Hz, 1H), 5.57–5.44
(m, 2H), 5.33 (dd, J¼17.2, 1.1 Hz, 1H), 5.28–5.16 (m, 5H), 4.71–4.65
(m, 1H), 4.15 (d, J¼13.8 Hz, 1H), 3.53 (d, J¼8.6 Hz, 1H), 3.47 (d,
J¼13.8 Hz, 1H), 3.28 (d, J¼10.9 Hz, 1H), 3.10 (d, J¼10.9 Hz, 1H), 2.70
(dd, J¼5.0, 13.7 Hz, 1H), 2.00 (ddd, J¼8.7, 10.8, 13.7 Hz, 1H); 13C NMR
1H), 5.80 (ddd, J¼17.1, 10.4, 6.6 Hz, 1H), 5.72 (dt, J¼5.7, 2.2 Hz, 1H),
5.30 (dt, J¼17.2, 1.2 Hz, 1H), 5.23–5.15 (m, 1H), 4.52–4.38 (m, 2H),
4.05 (d, J¼14.4 Hz, 1H), 3.82 (d, J¼5.2 Hz, 3H), 3.64–3.54 (m, 2H),
2.75 (ddd, J¼13.8, 5.5, 2.0 Hz, 1H), 2.64–2.43 (m, 2H), 2.12 (dt,
(125 MHz, CDCl3)
d
ppm 139.4, 137.3, 136.2, 136.0, 119.9, 118.1, 116.4,
J¼13.8, 9.9 Hz, 1H); 13C NMR (125 MHz, CDCl3)
d ppm 159.5, 135.9,
115.7, 85.7, 81.8, 66.6, 56.7, 44.7, 35.1; HRMS calculated for
135.1,130.4,130.2,126.8,118.0,114.1, 97.3, 80.1, 64.6, 63.8, 55.3, 45.4,
35.5, 35.2; HRMS calculated for C18H21NNaO4S (MþNa)þ 370.1089,
found 370.1087.
C14H19NNaO3S (MþNa)þ 304.0983, found 304.0947.
4.2.9. Sultam [(ꢁ) 13]
To a flame dried flask containing dry toluene (0.5 mL) wereadded
diene 12 (30 mg, 0.1 mmol) and N-phenylmaleimide (0.23 g,
0.13 mmol). The reaction mixture was heated at 85 ꢀC for 24 h. The
crude reaction mixture was concentrated under reduced pressure
and purified byflash chromatography (3:2 hexane/EtOAc) toyield 13
(38 mg, 8.3ꢃ10ꢂ5 mol, 83% yield) as a yellow oil. FTIR (neat): 1709,
4.2.12. Sultam [(ꢁ) 17]
FTIR (neat): 1514, 1303, 1247, 1145 cmꢂ1 1H NMR (500 MHz,
;
CDCl3)
d
ppm 7.31 (d, J¼8.7 Hz, 2H), 6.90–6.85 (m, 2H), 5.97–5.81
(m, 2H), 5.72 (dddd, J¼11.7, 9.5, 7.5, 6.4 Hz, 1H), 5.56–5.48 (m,
1H), 5.39 (ddd, J¼12.5, 4.3, 3.1 Hz, 2H), 5.27–5.20 (m, 1H), 5.00–
4.92 (m, 2H), 4.76 (dd, J¼11.0, 5.9 Hz, 1H), 4.42 (d, J¼15.8 Hz, 1H),
4.10 (d, J¼15.8, 1H), 3.84–3.78 (s, 3H), 3.55 (d, J¼8.4 Hz, 1H), 3.38
(dd, J¼7.4, 5.2 Hz, 1H), 2.75 (ddd, J¼13.6, 5.1, 0.9 Hz, 1H), 2.47–
2.38 (m, 1H), 2.34–2.26 (m, 1H), 2.02 (ddd, J¼13.6, 10.8, 8.5 Hz,
1498, 1383, 1309, 1147 cmꢂ1; 1H NMR (500 MHz, CDCl3)
d ppm 7.43
(dd, J¼8.0, 16.5 Hz, 2H), 7.36 (dd, J¼7.5, 15.2 Hz, 1H), 7.32–7.27 (m,
1H), 7.22 (d, J¼7.3 Hz, 1H), 5.94 (td, J¼10.8, 16.7 Hz, 2H), 5.80 (dddd,
J¼6.8, 10.4, 13.4, 17.0 Hz, 1H), 5.56–5.47 (m, 1H), 5.37 (dd, J¼17.2,
22.0 Hz,1H), 5.28–5.13 (m, 2H), 4.79–4.71 (m,1H), 3.81 (d, J¼14.1 Hz,
1H), 3.52 (d, J¼8. Hz,1H), 3.42–3.22 (m, 3H), 3.16 (dd, J¼5.5,10.8 Hz,
1H), 3.06 (dd, J¼3.0, 10.8 Hz, 1H), 2.76–2.64 (m, 3H), 2.47–2.32 (m,
1H); 13C NMR (125 MHz, CDCl3)
d ppm 159.5, 139.1, 136.8, 129.8,
118.1, 118.1, 117.1, 114.3, 88.5, 82.4, 66.9, 66.1, 55.7, 46.0, 35.1,
32.5; HRMS calculated for C20H25NNaO4S (MþNa)þ 398.1402,
found 398.1401.