Sodium Methoxide → Allyl (3,4-di-O-benzyl-alpha-L-rhamnopyranosyl)-(1->2)-3,4-di-O-benzyl-alpha-L-rhamnopyranoside

HRID 62293Notes

Reaction equation

HRID 62293 reaction equation
C[O-].[Na+].C([O:7][C@@H:8]1[C@H:13]([O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C@@H:12]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@H:11]([CH3:30])[O:10][C@H:9]1[O:31][C@@H:32]1[C@H:41]([O:42][CH2:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[C@@H:40]([O:50][CH2:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[C@H:39]([CH3:58])[O:38][C@H:33]1[O:34][CH2:35][CH:36]=[CH2:37])(=O)C>CO>[CH2:15]([O:14][C@@H:13]1[C@@H:12]([O:22][CH2:23][C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C@H:11]([CH3:30])[O:10][C@@H:9]([O:31][C@@H:32]2[C@H:41]([O:42][CH2:43][C:44]3[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=3)[C@@H:40]([O:50][CH2:51][C:52]3[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=3)[C@H:39]([CH3:58])[O:38][C@H:33]2[O:34][CH2:35][CH:36]=[CH2:37])[C@@H:8]1[OH:7])[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

4

Reactant 2

HCID 10942334Sodium MethoxideHCID 21633268Allyl (2-O-acetyl-3,4-di-O-benzyl-alpha-L-rhamnopyranosyl)-(1->2)-3,4-di-O-benzyl-alpha-L-rhamnopyranoside

Product 1

HCID 14353223Allyl (3,4-di-O-benzyl-alpha-L-rhamnopyranosyl)-(1->2)-3,4-di-O-benzyl-alpha-L-rhamnopyranosideYield 93%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A 1M solution of sodium methoxide in methanol (1.1 mL) was added to a solution of 322 (3.10 g, 4.13 mmol) in methanol. The mixture was stirred at rt for 3 h. The mixture was neutralised with Amberlite IR-120 (H+) resin, filtered and concentrated to give 323 (2.72 g, 93%) as a colourless syrup which crystallised on standing; mp 98-99° C.; lit. (Pinto, B. M.; Reimer, K. B.; Morissette, D. G.; Bundle, D. R. J. Org. Chem. 1989, 54, 2650-2656) mp 100° C. (hexane); [α]D−30° (c 0.5, CHCl3), lit. (Pinto, B. M.; Reimer, K. B.; Morissette, D. G.; Bundle, D. R. J. Org. Chem. 1989, 54, 2650-2656) [α]D−32.5° (c, 0.4, CHCl3); 1H NMR: δ 7.42-7.30 (m, 20H, Ph), 5.90-5.80 (m, 1H, All), 5.32-5.20 (m, 2H, All), 5.13 (d, 1H, J1,2=1.4 Hz, H-1A), 4.82 (d, 1H, J1,2=1.6 Hz, H-1B), 4.95-4.60 (m, 8H, CH2Ph), 4.20-4.12 (m, 1H, All), 4.19 (m, 1H, J2,3=3.2, J2,OH=1.8 Hz, H-2A),4.09 (d, 1H, J2,3=3.2 Hz, H-2B), 4.00-3.95 (m, 1H, All), 3.95 (dd, 1H, J3,4=9.4 Hz, H-3A), 3.93 (dd, 1H, J3,4=9.4 Hz, H-3B), 3.87 (dq, 1H, J4,5=9.4, J5,6=6.2 Hz, H-5A), 3.74 (dq, 1H, J4,5=9.4, J5,6=6.2 Hz, H-5B), 3.53 (pt, 1H, H-4A), 3.46 (pt, 1H, H-4B), 2.52 (d, 1H, OH), 1.35 (m, 6H, H-6A, 6B); 13C NMR: δ 138.4-117.1 (Ph, All), 101.2 (C-1A), 98.4 (C-1B), 80.8, 80.4 (2C, C-4A, 4B), 80.3 (C-3B), 80.0 (C-3A), 75.8, 75.7 (2C, CH2Ph), 75.0 (C-2B), 72.7, 72.6 (2C, CH2Ph), 69.1 (C-2A), 68.4 (C-5B), 68.3 (C-5A), 68.1 (All), 18.4, 18.3 (2C, C-6A, 6B). CI-MS for C43H50O9 (M, 710) m/z 728 [M+NH4]+.

Workup

  1. filtrationfiltered
  2. concentrationconcentrated

Sources & evidence

ORD record
ord-7614664de8514829a44b2d882fb7c052
Source dataset
uspto-grants-2016_09
Patent number
US09446109B2

Reaction notes

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