Boron trifluoride etherate → HCID 86744114, compound

HRID 2166290Notes

Reaction equation

HRID 2166290 reaction equation
C([O:9][CH2:10][C:11]1([O:42][C@H:41]([CH2:43][O:44][C:45](=[O:52])[C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@@H:31]([O:32]C(=O)C2C=CC=CC=2)[C@@H:21]1[O:22]C(=O)C1C=CC=CC=1)OC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[CH2:53]([Si](C)(C)C)[C:54]#[CH:55].B(F)(F)F.CCOCC>C(#N)C>[C:45]([O:44][CH2:43][C@@:41]1([O:42][C@H:11]([CH2:10][OH:9])[C@@H:21]([OH:22])[C@@H:31]1[OH:32])[CH:53]=[C:54]=[CH2:55])(=[O:52])[C:46]1[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=1

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 83378Trimethyl-2-propynylsilaneHCID 53661141HCID 53661141, compound

Product 1

HCID 86744114HCID 86744114, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

In accordance with Flowchart G, D-fructofuranose pentabenzoate 57 and propargyltrimethylsilane in acetonitrile at 0° C. are reacted with boron trifluoride etherate, giving 4,7-anhydro-4-C-[(benzoyloxy)methyl]-1,2,3-trideoxy-D-manno-octa-1,2-dienitol, tribenzoate 58, which is treated with sodium methoxide in methanol, giving 4,7-anhydro-1,2,3-trideoxy-4-C-(hydroxymethyl)-D-oluco (or D-manno)-octa-1,2-dienitol 59. Compound 59 is treated with cupric sulfate and sulfuric acid in acetone followed by sodium carbonate in pyridine, giving 4,7:41,5-dianhydro-1,2,3-trideoxy-4-C-[(1-hydroxy-1-methylethoxy)methyl]-D-manno-octa-1,2-dienitol 60 which is reacted with sodium hydride in dimethylformamide at 0° C. and then with 15 benzyl bromide and methanol, giving 4,7:41,5-dianhydro-1,2,3-trideoxy-4-C-[(1-hydroxy-1-methylethoxy)methyl]-6,8-bis-O-(phenylmethyl)-D-manno-octa-1,2-dienitol 61. Compound 61 is ozonized at -78° C. in dichloromethane containing pyridine, then treated with zinc dust and acetic acid, giving 2,5:21,3-dianhydro--2-C-[(1-hydroxy-1-methylethoxy)methyl]-4,6-bis-O-(phenylmethyl)-D-mannose 62, which is dissolved in diethyl phosphite and reacted with sodium ethoxide in ethanol, followed by sodium dihydrogen phosphate in dichloromethane, giving 2,5-anhydro-2-C-[(diethoxyphosphinyl)hydroxymethyl]-1,3-0-(1-m®thylethylidene)-4,6--bis-O-(phenylmethyl)-D-glucitol 63. Compound 63 is treated with diisopropylethylamine and 2-(trimethylsilyl)ethoxymethyl chloride in dichloromethane, giving 2,5-anhydro-2-C-[(diethoxyphosphinyl)[[2-(trimethylsilyl)ethoxy]methoxy]methyl]-1,3-O-(1-methylethylidene)--4,6-bis-O-(phenylmethyl)-D-glucitol 64, which is hydrogenated in methanol over palladium hydroxide on carbon, giving 2,5-anhydro-2-C-[(diethoxyphosphinyl)-[[2-(trimethylsilyl)ethoxy]methoxy]methyl]-1,3-O-(1-methylethylidene)-D-glucitol 65. Compound 65 is reacted with diphenyl phosphorochloridate in pyridine at 0° C., giving 2,5-anhydro-2-C-[(diethoxyphosphinyl)-[[2-(trimethylsilyl)ethoxy]methoxy]methyl]-1,3-O-(1-methylethylidene)-D-glucitol, 6-(diphenyl phosphate) 66, which is reacted with bromotrimethylsilane in dichloromethane, then hydrogenated in ethanol over platinum oxide, giving 2,5-anhydro-2-C-(hydroxyphosphonomethyl)-D-glucitol, 6-(dihydrogen phosphate) 67. ##STR16##

Sources & evidence

ORD record
ord-3409f176afd54ef6b5396684d5adc9d5
Source dataset
uspto-grants-1990_07
Patent number
US04943629

Reaction notes

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