Benzene → 2-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-4-O-(4-O-acetyl-2,6-di-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-galactopyranoside

HRID 2626

Reaction equation

HRID 2626 reaction equation
[C:1]([O:9][C@@H:10]1[C@@H:22]([O:23][C@@H:24]2[O:53][C@@H:52]([CH3:54])[C@@H:43]([O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[C@@H:34]([O:35][CH2:36][C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)[C@@H:25]2[O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@H:21]([O:55][C@@H:56]2[O:72][C@H:71]([CH2:73][O:74][C:75](=[O:82])[C:76]3[CH:81]=[CH:80][CH:79]=[CH:78][CH:77]=3)[C@H:69]([OH:70])[C@H:67]([OH:68])[C@H:57]2[O:58][C:59](=[O:66])[C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[C@@H:20]([CH2:83][O:84][C:85](=[O:92])[C:86]2[CH:91]=[CH:90][CH:89]=[CH:88][CH:87]=2)[O:19][C@H:11]1[O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C=CC(S(O)(=O)=[O:100])=CC=1.[CH:104]1[CH:109]=CC=CC=1>C(OCC)(OCC)(OCC)C.C(N(CC)CC)C>[C:1]([O:9][C@@H:10]1[C@@H:22]([O:23][C@@H:24]2[O:53][C@@H:52]([CH3:54])[C@@H:43]([O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[C@@H:34]([O:35][CH2:36][C:37]3[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=3)[C@@H:25]2[O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@@H:21]([O:55][C@@H:56]2[O:72][C@H:71]([CH2:73][O:74][C:75](=[O:82])[C:76]3[CH:77]=[CH:78][CH:79]=[CH:80][CH:81]=3)[C@H:69]([O:70][C:109](=[O:100])[CH3:104])[C@H:67]([OH:68])[C@H:57]2[O:58][C:59](=[O:66])[C:60]2[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=2)[C@@H:20]([CH2:83][O:84][C:85](=[O:92])[C:86]2[CH:87]=[CH:88][CH:89]=[CH:90][CH:91]=2)[O:19][C@H:11]1[O:12][CH2:13][CH2:14][Si:15]([CH3:17])([CH3:18])[CH3:16])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 241BenzeneHCID 6101p-Toluenesulfonic acidHCID 536678922-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-beta-D-galactopyranosyl)-beta-D-glucopyranoside

Product 1

HCID 541262422-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-4-O-(4-O-acetyl-2,6-di-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-galactopyranosideYield 89%

Reagents, catalysts & solvents 2

HCID 8471TriethylamineCatalystHCID 66221Triethyl orthoacetateSolvent

Procedure

A solution of compound 10a (1.87 g), in a mixture of benzene (50 mL) and triethyl orthoacetate (50 mL), containing 4-toluenesulfonic acid (0.25 g) was stirred for 1 h at room temperature. The acid was then neutralized with a few drops of triethylamine, and the mixture evaporated to dryness. The residue was mixed with 80% aqueous acetic acid (100 mL) and the mixture stirred for 40 min at room temperature. Processing as described for 10b (to give 11b), gave the title compound 11a (1.86 g,89%); a white amorphous solid; [α]D -2.7° (c, 1.1, chloroform). 13C NMR (CDCl3): δ171.03 (CH3CO), 166.78, 166.35, 166.18, 165.02 (4×PhCO), 101.27, 101.09 (C-1, C-1'), 98.17 (C-1 fuc), 80.10, 78.20 (C-3, C-4), 74.67, 73.54, 73.30 (3×PhCH2), 67.86 (OCH2CH2Si), 63.31, 61.42 (C-6, C-6'), 21.21 (CH3 CO), 18.47 (OCH2CH2Si), and 17.53 (C-6 fuc); negative ion LSIMS: 1470.8 (M+mNBA)-, 1363.7 (M+NO2)-.

Workup

  1. customthe mixture evaporated to dryness
  2. additionThe residue was mixed with 80% aqueous acetic acid (100 mL)
  3. stirringthe mixture stirred for 40 min at room temperature

Sources & evidence

ORD record
ord-efe1cb2656924866b2ad6f8e5b445bf1
Source dataset
uspto-grants-1998_03
Patent number
US05728685

Linked notes

Loading…