1-Octanethiol → 2-(Octylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

HRID 653325Notes

Reaction equation

HRID 653325 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:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[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]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[CH2:48]([SH:56])[CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55].C(=O)([O-])[O-].[Cs+].[Cs+].C(O[C@@H]1[C@@H](OC(=O)C)[C@@H](OC(=O)C)[C@@H](COC(=O)C)O[C@H]1OCCSCCCCCCCC)(=O)C>[Cl-].C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C1C=CC=CC=1.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:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[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]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9][S:56][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 81441-OctanethiolHCID 10796Cesium carbonateHCID 228870902-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosideHCID 542299382-(Octylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

Product 1

HCID 538927502-(Octylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosideYield 47.5%

Reagents, catalysts & solvents 3

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

Compound 15 (484 mg; 0.65 mmol), octanethiol (110 mg; 0.75 mmol; 130 μl), methyltrioctylammonium chloride (ca 10 mg) and cesium carbonate (245 mg; 0.75 mmol) were dissolved in benzene (1 ml) and water (1 ml). The reaction mixture was treated as for compound 21. Chromatography gave the title compound (23) (250 mg) and starting compound 15 (160 mg). Yield (based on consumed 15): 71%; [α]D21 +65.3° (c 1.4; CHCl3); 1H-NMR (CDCl3, TMS) δ 5.57 (dd, 1H, J4',5' =1 Hz, H4'), 5.39 (dd, 1H, J2', 3'=11 Hz, J3',4' =3.5 Hz, H3'), 5.20 (dd, H1, J1', 2' =3.5 Hz, H2'), 5.19 (dd, 1H, J2,3 =11 Hz, J1,2 =7.5 Hz, H2), 5.01 (d, 1H, J1',2' =3.5 Hz, H1'), 4.81 (dd, 1H, J3,4 =3 Hz, H3), 4.51 (d, 1H, J1,2 =7.5 Hz, H1), 2.73, 2.53 (t, 2H each, J=7 Hz, CH2 --S), 2.13, 2.11, 2.08, 2.08, 2.07, 2.04, 1.99 (s, 3H each, CH3 --CO) ppm. 13C-NMR (CDCl3, TMS) 170.7, 170.6, 170.5, 170.4, 170.1, 169.8, 169.1 (CO), 101.2 (Cl), 99.4 (Cl'), 77.1, 72.7, 71.9, 68.6, 68.6, 67.8, 67.4, 67.1 (C2-C5, C2'-C5'), 69.6 (O--CH2 --CH2 --S), 62.0, 60.5 (C6, C6'), 32.6, 31.8, 31.3, 29.8, 29.2, 28.8, 22.7 (aglycon-CH2), 21.0, 20.8, 20.7 (CH3 --CO), 14.1 (CH3 --CH2) ppm.

Sources & evidence

ORD record
ord-5bd2d815e70045b58ccd9587f13fbb9f
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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