Methyl 3-mercaptopropionate → 2-(2-Methoxycarbonylethylthio)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 653344Notes

Reaction equation

HRID 653344 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].[SH:88][CH2:89][CH2:90][C:91]([O:93][CH3:94])=[O:92]>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:88][CH2:89][CH2:90][C:91]([O:93][CH3:94])=[O:92])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 18050Methyl 3-mercaptopropionateHCID 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 186083042-(2-Methoxycarbonylethylthio)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 79%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Compound 93 (4.00 g, 3.0 mmol), methyl 3-mercaptopropionate (0.546 g, 0.49 ml, 4.5 mmol) cesium carbonate (1.17 g, 3.6 mmol) and N,N-dimethylformamide (25 ml), were stirred at room temperature until 93 had been consumed (7 h; TLC; SiO2, ethyl acetate:isooctane 4:1). The solvent was removed and the residue was chromatographed (SiO2, ethyl acetate:isooctane 3:1) to give 94 (3.22 g, 78%). [α]D25 +102° (c 1.0, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.36, 5.28, 5.19 (3d, each 1H, J=3.8, 4.1 and 3.7 Hz, H1', H1", H1"'), 4.57 (d, 1H, J=7.9 Hz, H1), 3.71 (s, 3H, MeO), 2.81, 2.71, 2.61 (3t, each 2H, J=6.7 Hz, CH2 --S--CH2 and CH2 --CO). 13C-NMR (CDCl3, Me4Si) δ 100.2 (Cl), 95.8, 95.6, 95.2 (Cl', Cl", Cl"'), 75.1, 73.7, 72.6, 72.0 71.9, 71.7, 70.7, 70.3, 70.0, 69.8, 69.6, 69.3, 69.2, 68.8, 68.4, 67.3, 65.2, 63.0, 62.9, 61.7, 60.3, 51.7, 34.6, 31.3, 27.2, 20.8-20.5.

Workup

  1. customhad been consumed (7 h; TLC; SiO2, ethyl acetate:isooctane 4:1)
  2. customThe solvent was removed
  3. customthe residue was chromatographed (SiO2, ethyl acetate:isooctane 3:1)

Sources & evidence

ORD record
ord-2e3c75b13b494d4fb5f8a1fb3d4ea5ed
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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