Cesium carbonate → 2-(Octadecylthio)ethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

HRID 653336Notes

Reaction equation

HRID 653336 reaction equation
[C:1]([O:4][C@H:5]1[C@H:14]([O:15][C@@H:16]2[O:53][C@H:52]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[C@H:27]([O:28][C@H:29]3[O:46][C@H:45]([CH2:47][O:48][C:49](=[O:51])[CH3:50])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]3[O:31][C:32](=[O:34])[CH3:33])[C@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]2[O:18][C:19](=[O:21])[CH3:20])[C@@H:13]([CH2:59][O:60][C:61](=[O:63])[CH3:62])[O:12][C@@H:7]([O:8][CH2:9][CH2:10]Br)[C@@H:6]1[N:64]1[C:68](=[O:69])[C:67]2=[CH:70][CH:71]=[CH:72][CH:73]=[C:66]2[C:65]1=[O:74])(=[O:3])[CH3:2].[CH2:75]([SH:93])[CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH2:87][CH2:88][CH2:89][CH2:90][CH2:91][CH3:92].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[C:1]([O:4][C@H:5]1[C@H:14]([O:15][C@@H:16]2[O:53][C@H:52]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[C@H:27]([O:28][C@H:29]3[O:46][C@H:45]([CH2:47][O:48][C:49](=[O:51])[CH3:50])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]3[O:31][C:32](=[O:34])[CH3:33])[C@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]2[O:18][C:19](=[O:21])[CH3:20])[C@@H:13]([CH2:59][O:60][C:61](=[O:63])[CH3:62])[O:12][C@@H:7]([O:8][CH2:9][CH2:10][S:93][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][CH2:85][CH2:86][CH2:87][CH2:88][CH2:89][CH2:90][CH2:91][CH3:92])[C@@H:6]1[N:64]1[C:68](=[O:69])[C:67]2=[CH:70][CH:71]=[CH:72][CH:73]=[C:66]2[C:65]1=[O:74])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 179051-OctadecanethiolHCID 867416432-Bromoethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

Product 1

HCID 186083192-(Octadecylthio)ethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranosideYield 91%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Compound 78 (1.68 g, 1.5 mmol), octadecanethiol (0.81 g, 2.8 mmol), cesium carbonate (0.50 g, 1.53 mmol) and N,N-dimethylformamide (11 ml) were stirred at room temperature for 7.5 h and worked up as above for 79. The resulting residue was chromatographed (SiO2 -column, 5×18 cm; ethyl acetate:isooctane 2:1 followed by 4:1 and finally ethyl acetate) to give 80 (1.80 g, 91%). Crystallization from methanol gave an analytical sample with mp 150°-152°, [α]D21 +47° (c 0.6, chloroform). 1H-NMR (CDCl3, Me4Si) δ 7.93-7.72 (4H), 5.75 (m, 1H, H3), 5.58 (bd, 1H, J~3 Hz, H4"), 5.42 (d, 1H, J=8 Hz, H1), 5.38 (dd, 1H, J=11 and 3.5 Hz, H2"), 5.16 (dd, 1H, J=11 and 3.5 Hz, H3"), 5.13 (dd, 1H, J=11 and 8 Hz, H2'), 4.98 (d, 1H, J=3.5 Hz, H1"), 4.74 (dd, 1H, J=11 and 2.5 Hz, H3'), 4.63-4.34 (4H, inter alia H1'), 4.58 (d, 1H, J=8 Hz, H1'), 4.29-3.57 (11H), 2.55 (t, 2H, J=7 Hz, CH2S), 2.31 (t, 2H, J=7 Hz, CH2S), 2.15, 2.12, 2.07 (6H), 2.064, 2.058, 2.04, 1.96, 1.95, 1.40-1.15 (bs), 0.88 (t, 3H, J=6.5 Hz, CH3). 13C (CDCl3, Me4Si) δ 170.7, 170.5 (3C), 170.4 170.0, 169.7, 169.5, 168.9, 168.2 (broad, 2C), 134.2 (2C), 134.0 (2C), 123.5 (2C), 101.0 (d, J=160 Hz, Cl' or Cl), 99.6 (d, J=173 Hz, Cl"), 98.1 (d, J=160 Hz, Cl or Cl'), 77.8, 72.7, 72.6, 71.62, 71.56, 69.7 (OCH2CH2), 69.0, 68.8, 67.9, 67.1 (2C), 62.4 (CH2), 61.1 (CH2), 60.2 (CH2), 54.2 (C2), 32.4-22.7 (CH2), 21.0, 20.9, 20.74, 20.68 (2C), 20.64, 20.57, 20.51, 20.45, 14.14.

Workup

  1. customThe resulting residue was chromatographed (SiO2 -column, 5×18 cm

Sources & evidence

ORD record
ord-a7d2cf4fd6cb42c58c34c74ed12155ab
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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