Synthèse de CF2-carbasucres par cyclisation radicalaire et ... - TEL

tel-00559649, version 1 - 26 Jan 2011
Experimental section
(R)-(+)-2-Methyl-propane-2-sulfinic acid (3-(R),4-(R)-bis-benzyloxy-1,1-difluoro-5-
methyl-cyclopentyl)-amide (101):
6
BnO
O
F F S
NH
5
4
1 2
3
OBn
BnO
O
F F S
NH
1
5 2
4 3
OBn
101 (Major) 101' (minor)
Rf = 0.52 (30% EtOAc in cyclohexane). 1 H NMR (300 MHz, CDCl3) δ 7.43-7.23 (m, 10H, Ph),
4.75 (d, J = 18.8 Hz, 1H, M, CH2Ph), 4.71 (d, J = 18.8 Hz, 1H, m, CH2Ph), 4.59-4.48 (m, 2H,
CH2Ph), 4.41 (d, J = 18.8 Hz, 1H, M, CH2Ph), 4.14-3.97 (m, 3H, H2-3-NH), 3.70 (d, J = 6.1 Hz,
1H, m, H4), 3.53 (d, J = 7.2 Hz, 1H, M, H4), 2.58-2.49 (m, 1H, m, H5), 2.32-2.06 (m, 1H, M,
H5), 1.25 (s, 9H, C(CH3)3), 1.16 (d, J = 7.1 Hz, 3H, M, H6), 1.06 (d, J = 7.1 Hz, 3H, m, H6). 19 F
NMR (282.5 MHz, CDCl3) δ -106.6 (d, J = 234.1 Hz, 1F), -120.3 (d, J = 232.7 Hz, 1F). 13 C
NMR (75.5 MHz, CDCl3) δ 136.6, 136.5, 136.3, 136.2, 128.9, 128.8, 128.7, 128.6, 128.4 (x2),
128.2 (x2), 128.0, 127.9 (Ph), 126.1 (t, J = 256.1 Hz, C1), 86.9 (d, J = 7.2 Hz, M, C4), 80.6 (m,
C4), 80.5, 80.4, 80.3, 80.2, 80.0 (C2 or C3), 73.0 (x2), 72.4, 72.3 (CH2Ph), 61.6 (d, J = 19.1
Hz), 61.2 (d, J = 19.1 Hz), 60.8 (d, J = 19.1 Hz), 60.5 (d, J = 19.1 Hz, C3 or C2), 56.8, 56.7
(C(CH3)3), 43.7 (t, J = 21.8 Hz, M, C5), 41.9 (t, J = 23.0 Hz, m, C5), 22.8 (C(CH3)3), 11.0 (d, J
= 6.9 Hz, M, C6), 7.3 (d, J = 7.4 Hz, m, C6). MS (ESI+): m/z = 452.20 ([M+H] + ), 903.0
([2M+H] + ). Anal. Calcd. for C24H31F2NO3S: C, 63.83; H, 6.92; N, 3.10; S, 7.10. Found: C,
63.91; H, 7.26; N, 3.09; S, 6.78.
(S)-(-)-2-Methyl-propane-2-sulfinic acid (3-(R),4-(R)-bis-benzyloxy-1,1-difluoro-5-
methyl-cyclopentyl)-amide (102):
The same procedure was applied to 100 (149 mg, 0.25 mmol). Purification by column
chromatography using cyclohexane/EtOAc (95:05 to 80:20) as eluent afforded the desired
product 102 (87 mg, 78%, d.r. = 90:10).
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