Cesium carbonate → 2-(Octadecylthio)ethyl 2,3,6-tri-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-alpha-D-glucopyranosyl}-beta-D-glucopyranoside

HRID 653346Notes

Reaction equation

HRID 653346 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C@H:20]2[O:77][C@H:76]([CH2:78][O:79][C:80](=[O:82])[CH3:81])[C@@H:31]([O:32][C@H:33]3[O:50][C@H:49]([CH2:51][O:52][C@H:53]4[O:70][C@H:69]([CH2:71][O:72][C:73](=[O:75])[CH3:74])[C@@H:64]([O:65][C:66](=[O:68])[CH3:67])[C@H:59]([O:60][C:61](=[O:63])[CH3:62])[C@H:54]4[O:55][C:56](=[O:58])[CH3:57])[C@@H:44]([O:45][C:46](=[O:48])[CH3:47])[C@H:39]([O:40][C:41](=[O:43])[CH3:42])[C@H:34]3[O:35][C:36](=[O:38])[CH3:37])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:83][O:84][C:85](=[O:87])[CH3:86])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[CH2:88]([SH:106])[CH2:89][CH2:90][CH2:91][CH2:92][CH2:93][CH2:94][CH2:95][CH2:96][CH2:97][CH2:98][CH2:99][CH2:100][CH2:101][CH2:102][CH2:103][CH2:104][CH3:105].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C@H:20]2[O:77][C@H:76]([CH2:78][O:79][C:80](=[O:82])[CH3:81])[C@@H:31]([O:32][C@H:33]3[O:50][C@H:49]([CH2:51][O:52][C@H:53]4[O:70][C@H:69]([CH2:71][O:72][C:73](=[O:75])[CH3:74])[C@@H:64]([O:65][C:66](=[O:68])[CH3:67])[C@H:59]([O:60][C:61](=[O:63])[CH3:62])[C@H:54]4[O:55][C:56](=[O:58])[CH3:57])[C@@H:44]([O:45][C:46](=[O:48])[CH3:47])[C@H:39]([O:40][C:41](=[O:43])[CH3:42])[C@H:34]3[O:35][C:36](=[O:38])[CH3:37])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:83][O:84][C:85](=[O:87])[CH3:86])[O:11][C@H:6]1[O:7][CH2:8][CH2:9][S:106][CH2:88][CH2:89][CH2:90][CH2:91][CH2:92][CH2:93][CH2:94][CH2:95][CH2:96][CH2:97][CH2:98][CH2:99][CH2:100][CH2:101][CH2:102][CH2:103][CH2:104][CH3:105])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 179051-OctadecanethiolHCID 867416462-Bromoethyl 2,3,6-tri-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-alpha-D-glucopyranosyl]-beta-D-glucopyranoside

Product 1

HCID 867416482-(Octadecylthio)ethyl 2,3,6-tri-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-alpha-D-glucopyranosyl}-beta-D-glucopyranosideYield 46.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Compound 93 (265 mg, 0.2 mmol), octadecanethiol (86 mg, 0.3 mmol), cesium carbonate (79 mg, 0.24 mmol) and N,N-dimethylformamide (10 ml) were stirred at room temperature until 93 had been consumed (48 h; TLC, SiO2, ethyl acetate:isooctane 4:1). The solvent was removed and the residue was chromatographed (SiO2, ethyl acetate:isooctane 1:1) to give 96 (142 mg, 44%). [α]D25 +93° (c 0.5, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.30, 5.22, 5.12 (3d, each 1H, J=4.0, 4.2 and 3.7 Hz, H1', H1", H1"'), 4.51 (d, 1H, J=7.9 Hz, H1), 2.62, 2.46 (2t, each 2H, J=7.0 Hz, CH2 --S--CH2). 13C-NMR (CDCl3, Me4Si) δ 170.5-169.1 (CO), 100.2 (Cl), 95.7, 95.6, 95.2 (Cl', Cl", Cl"'), 75.1, 73.7, 72.6, 72.0, 71.6, 70.6, 70.3, 70.0, 69.8, 69.7, 69.6, 69.3, 69.2, 68.8, 68.4, 68.3, 67.3, 65.2, 63.0, 62.9, 61.7, 32.4, 31.8, 31.2, 29.6, 29.5, 29.5, 29.4, 29.2, 29.1, 28.7, 22.6, 20.8-20.5, 14.0.

Workup

  1. customhad been consumed (48 h; TLC, SiO2, ethyl acetate:isooctane 4:1)
  2. customThe solvent was removed
  3. customthe residue was chromatographed (SiO2, ethyl acetate:isooctane 1:1)

Sources & evidence

ORD record
ord-85c6038c11c1415f981af5459a4fd13c
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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