M. Penso, D. Albanese, D. Landini, V. Lupi, G. Tricarico
FULL PAPER
3
3
3
8.7 Hz, 2 H, 6-H), 7.09 (d, JH,H ϭ 8.7 Hz, 2 H, 5-H), 7.64Ϫ8.02 [d, JH,H ϭ 7.9 Hz, 1 H, C(p-SO2)ϪH], 7.91 [d, JH,H ϭ 7.9 Hz, 1
[m, 8 H, C(nosyl)ϪH] ppm. C22H19N3O11S2 (565.05): calcd. C
46.72, H 3.39, N 7.43; found C 46.61, H 3.24, N 7.46.
H, C(p-SO2)ϪH], 7.93 [d, 3JH,H ϭ 7.9 Hz, 1 H, C(p-CF3)ϪH], 7.97
[d, 3JH,H ϭ 7.9 Hz, 1 H, C(p-CF3)ϪH], 8.01 [s, 1 H, C(o-SO2)ϪH],
8.08 [s, 1 H, C(o-SO2)ϪH] ppm. 19F NMR (282 MHz, CDCl3,
25 °C): δ ϭ Ϫ63.33 (s, CF3) ppm. C24H19F6NO7S2 (611.05): calcd.
C 47.14, H 3.13, N 2.29; found C 47.00, H 3.02, N 2.36.
5b: M.p. 132.5 °C. [α]2D0 ϭ ϩ4.1 (c ϭ 1, MeOH). 1H NMR
(300 MHz, CDCl3, 25 °C): δ ϭ 2.40 [s, 3 H, CH3(Tol)], 2.94 (υA-
ABXsystem, JAX ϭ 6.1, JAB ϭ 14.1 Hz, 1 H, 3-H), 2.96 (υB-ABXsys-
5f: Oil. [α]2D0 ϭ Ϫ17.6 (c ϭ 1, CHCl3). 1H NMR (300 MHz, CDCl3,
25 °C): δ ϭ 2.94 (υA-ABXsystem, JAX ϭ 8.0, JAB ϭ 14.0 Hz, 1 H,
3-H), 3.13 (υB-ABXsystem, JBX ϭ 4.7, JAB ϭ 14.0 Hz, 1 H, 3-H),
3.73 (s, 3 H, COOCH3), 4.45 (υX-ABXsystem, 1 H, 2-H), 5.21 (s, 1
tem, JBX ϭ 5.7, JAB ϭ 14.1 Hz, 1 H, 3-H), 3.48 (s, 3 H, COOCH3),
3
4.16 (υX-ABXsystem, 1 H, 2-H), 4.93 (s, 1 H, OH), 5.02 (d, JH,H
ϭ
3
9.1 Hz, 1 H, NH), 6.69 (d, JH,H ϭ 8.5 Hz, 2 H, 6-H), 6.92 (d,
3JH,H ϭ 8.5 Hz, 2 H, 5-H), 7.24 [d, JH,H ϭ 8.2 Hz, 2 H, C(m-
3
3
3
3
H, OH), 5.69 (d, JH,H ϭ 9.4 Hz, 1 H, NH,), 6.66 (d, JH,H
ϭ
SO2)ϪH], 7.63 [d, JH,H ϭ 8.2 Hz, 2 H, C(o-SO2)ϪH] ppm.
8.3 Hz, 2 H, 6-H), 6.95 (d, JH,H ϭ 8.3 Hz, 2 H, 5-H) ppm. 19F
3
C17H19NO5S (349.10): calcd. C 58.44, H 5.48, N 4.01; found C
58.31, H 5.35, N 4.08.
NMR (282 MHz, CDCl3, 25 °C): δ ϭ Ϫ136.56 [d, 3JFF ϭ 20.1 Hz,
3
2 F, C(o-SO2)ϪF], Ϫ146.66 [t, JFF ϭ 20.9 Hz, 1 F, C(p-SO2)ϪF],
Ϫ150.56 [dd, JFF ϭ 20.9, 20.1 Hz, 2 F, C(m-SO2)ϪF] ppm.
1
5c: M.p. 168.5Ϫ170 °C. [α]2D0 ϭ Ϫ20.7 (c ϭ 1, MeOH). H NMR
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(300 MHz, CDCl3, 25 °C): δ ϭ 2.93 (υA-ABXsystem, JAX ϭ 7.3,
C16H12F5NO5S (425.33): calcd. C 45.18, H 2.84, N 3.29; found C
45.35, H 2.93, N 3.16.
JAB ϭ 14.1 Hz, 1 H, 3-H), 3.05 (υB-ABXsystem, JBX ϭ 5.3, JAB
ϭ
14.0 Hz, 1 H, 3-H), 3.61 (s, 3 H, COOCH3), 4.20 (υX-ABXsystem, 1
8a: M.p. 164.1Ϫ164.8 °C. [α]2D5 ϭ Ϫ143.9 (c ϭ 0.5, THF). 1H NMR
(300 MHz, CDCl3/[D6]DMSO, 10:1, 25 °C): δ ϭ 3.62 (s, 3 H, CO-
OCH3), 5.19 (d, 3JH,H ϭ 8.2 Hz, 1 H, 2-H), 5.54 (s, 1 H, OH), 6.60
3
H, 2-H), 4.82 (s, 1 H, OH), 5.19 (d, JH,H ϭ 9.3 Hz, 1 H, NH),
3
3
6.66 (d, JH,H ϭ 8.4 Hz, 2 H, 6-H), 6.90 (d, JH,H ϭ 8.4 Hz, 2 H,
3
3
5-H), 7.86 [d, JH,H ϭ 8.8 Hz, 2 H, C(o-SO2)ϪH], 8.24 [d, JH,H ϭ
8.8 Hz, 2 H, C(o-NO2)ϪH] ppm. C16H16N2O7S (380.07): calcd. C
50.52, H 4.24, N 7.36; found C 50.44, H 4.16, N 7.40.
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(d, 3JH,H ϭ 8.2 Hz, 1 H, NH,), 6.65 (d, JH,H ϭ 8.6 Hz, 2 H, 5-H),
3
3
7.08 (d, JH,H ϭ 8.6 Hz, 2 H, 4-H), 7.50 [ddd, JH,H ϭ 7.6, 7.6,
4JH,H ϭ 1.4 Hz, 1 H, C(p-SO2)ϪH], 7.62 [ddd, JH,H ϭ 7.8, 7.6,
3
6c: M.p. 161.8Ϫ162.7 °C. [α]2D0 ϭ ϩ17.2 (c ϭ 1, CHCl3). 1H NMR
(300 MHz, CDCl3, 25 °C): δ ϭ 2.93 (υA-ABXsystem, JAX ϭ 7.3,
4JH,H ϭ 1.6 Hz, 1 H, C(p-NO2)ϪH], 7.70 [dd, 3JH,H ϭ 7.6, 4JH,H ϭ
3
4
1.6 Hz, 1 H, C(o-SO2)ϪH], 7.81 [dd, JH,H ϭ 7.8, JH,H ϭ 1.4 Hz,
1 H, C(o-NO2)ϪH] ppm. C15H14N2O7S (366.05): calcd. C 49.18,
H 3.85, N 7.65; found C 49.05, H 3.80, N 7.72.
JAB ϭ 14.1 Hz, 1 H, 3-H), 3.05 (υB-ABXsystem, JBX ϭ 5.3, JAB
ϭ
14.0 Hz, 1 H, 3-H), 3.62 (s, 3 H, COOCH3), 4.20 (υX-ABXsystem, 1
3
3
H, 2-H), 5.21 (d, JH,H ϭ 9.0 Hz, 1 H, NH), 6.93 (d, JH,H
ϭ
8b: M.p. 150.0Ϫ150.4 °C. [α]2D5 ϭ Ϫ97.6 (c ϭ 1, MeOH). 1H NMR
(300 MHz, [D6]DMSO, 25 °C): δ ϭ 2.35 [s, 3 H, CH3(Tol)], 3.41
(s, 3 H, COOCH3), 4.83 (s, 1 H, 2-H), 6.43 (br. s, 1 H, NH), 6.64
3
8.6 Hz, 2 H, 6-H), 7.10 (d, JH,H ϭ 8.6 Hz, 2 H, 5-H), 7.93 [d,
3JH,H ϭ 8.8 Hz, 2 H, C(o-SO2)ϪH], 8.02 [d, JH,H ϭ 8.8 Hz, 2 H,
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C(o-SO2)ϪH], 8.32 [d, 3JH,H ϭ 8.8 Hz, 2 H, C(o-NO2)ϪH], 8.39 [d,
3JH,H ϭ 8.8 Hz, 2 H, C(o-NO2)ϪH] ppm. C22H19N3O11S2 (565.05):
calcd. C 46.72, H 3.39, N 7.43; found C 46.85, H 3.50, N 7.18.
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3
(d, JH,H ϭ 8.6 Hz, 2 H, 5-H), 7.04 (d, JH,H ϭ 8.6 Hz, 2 H, 4-H),
3
3
7.30 [d, JH,H ϭ 8.2 Hz, 2 H, C(m-SO2)ϪH], 7.60 [d, JH,H
ϭ
8.2 Hz, 2 H, C(o-SO2)ϪH], 8.21 (s, 1 H, OH) ppm. C16H17NO5S
(335.08): calcd. C 57.30, H 5.11, N 4.18; found C 57.41, H 5.19,
N 4.09.
5d: M.p. 137Ϫ138 °C. [α]2D0 ϭ Ϫ2.4 (c ϭ 1, MeOH). 1H NMR
(300 MHz, CDCl3, 25 °C): δ ϭ 2.93 (υA-ABXsystem, JAX ϭ 7.2,
JAB ϭ 14.0 Hz, 1 H, 3-H), 3.03 (υB-ABXsystem, JBX ϭ 5.2, JAB
ϭ
8c: M.p. 178Ϫ181 °C. [α]2D0 ϭ Ϫ98.5 (c ϭ 1, THF). 1H NMR
(300 MHz, CDCl3, 25 °C): δ ϭ 3.64 (s, 3 H, COOCH3), 4.84 (br.
14.0 Hz, 1 H, 3-H), 3.54 (s, 3 H, COOCH3), 4.16 (υX-ABXsystem, 1
3
H, 2-H), 5.09 (s, 1 H, OH), 5.26 (d, JH,H ϭ 9.1 Hz, 1 H, NH,),
3
3
3
3
s, 1 H, OH), 5.10 (d, JH,H ϭ 6.0 Hz, 1 H, 2-H), 5.82 (d, JH,H
ϭ
6.65 (d, JH,H ϭ 8.3 Hz, 2 H, 6-H), 6.89 (d, JH,H ϭ 8.3 Hz, 2 H,
5-H), 7.68 [d, 3JH,H ϭ 8.3 Hz, 2 H, C(o-CF3)ϪH], 7.82 [d, 3JH,H ϭ
8.3 Hz, 2 H, C(o-SO2)ϪH] ppm. 19F NMR (282 MHz, CDCl3,
25 °C): δ ϭ Ϫ63.52 (s, CF3) ppm. C17H16F3NO5S (403.07): calcd.
C 50.62, H 4.00, N 3.47; found C 50.50, H 4.11, N 3.28.
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6.0 Hz, 1 H, NH), 6.65 (d, JH,H ϭ 8.6 Hz, 2 H, 5-H), 7.01 (d,
3JH,H ϭ 8.6 Hz, 2 H, 4-H), 7.79 [d, JH,H ϭ 8.8 Hz, 2 H, C(o-
3
3
SO2)ϪH], 8.18 [d, JH,H ϭ 8.8 Hz, 2 H, C(o-NO2)ϪH] ppm.
C15H14N2O7S (366.05): calcd. C 49.18, H 3.85, N 7.65; found C
49.15, H 3.78, N 7.60.
5e: Wax. [α]2D0 ϭ Ϫ7.7 (c ϭ 1, CHCl3). 1H NMR (300 MHz, CDCl3,
25 °C): δ ϭ 2.94 (υA-ABXsystem, JAX ϭ 6.7, JAB ϭ 14.0 Hz, 1 H,
3-H), 3.01 (υB-ABXsystem, JBX ϭ 5.5, JAB ϭ 14.0 Hz, 1 H, 3-H),
Acknowledgments
This work was supported by Consiglio Nazionale delle Ricerche
(Italy) and MURST (Rome) ‘‘Progetto Nazionale Stereoselezione
in Chimica Organica: Metodologie e Applicazioni’’.
3.51 (s, 3 H, COOCH3), 4.22 (υX-ABXsystem, 1 H, 2-H), 5.51 (d,
3
3JH,H ϭ 9.1 Hz, 1 H, NH), 5.83 (s, 1 H, OH), 6.65 (d, JH,H
ϭ
3
8.3 Hz, 2 H, 6-H), 6.88 (d, JH,H ϭ 8.3 Hz, 2 H, 5-H), 7.56 [t,
3JH,H ϭ 7.7 Hz, 1 H, C(m-CF3)ϪH], 7.77 [d, JH,H ϭ 7.7 Hz, 1 H,
3
3
C(p-SO2)ϪH], 7.88 [d, JH,H ϭ 7.7 Hz, 1 H, C(p-CF3)ϪH], 8.01 [s,
1 H, C(o-SO2)ϪH] ppm. 19F NMR (282 MHz, CDCl3, 25 °C): δ ϭ
Ϫ63.28 (s, CF3) ppm. C17H16F3NO5S (403.07): calcd. C 50.62, H
4.00, N 3.47; found C 50.48, H 4.14, N 3.31.
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6e: Oil. [α]2D0 ϭ ϩ11.0 (c ϭ 0.82, CHCl3). 1H NMR (300 MHz,
CDCl3, 25 °C): δ ϭ 3.00 (υA-ABXsystem, JAX ϭ 7.2, JAB ϭ 13.9 Hz,
1 H, 3-H), 3.09 (υB-ABXsystem, JBX ϭ 5.5, JAB ϭ 13.9 Hz, 1 H, 3-
H), 3.49 (s, 3 H, COOCH3), 4.19 (υX-ABXsystem, 1 H, 2-H), 5.21
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3
3
[2d]
(d, JH,H ϭ 9.3 Hz, 1 H, NH), 6.87 (d, JH,H ϭ 8.5 Hz, 2 H, 6-H),
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S. C. Miller, T. S.
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3
7.05 (d, JH,H ϭ 8.5 Hz, 2 H, 5-H), 7.61 [t, JH,H ϭ 7.9 Hz, 1 H,
C(m-CF3)ϪH], 7.70 [t, JH,H ϭ 7.9 Hz, 1 H, C(m-CF3)ϪH], 7.81
3
T. Fukuyama, C.-K. Jow, M. Cheung, Tetrahedron Lett.
4516
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim