Boron trifluoride etherate → HCID 70360326, compound

HRID 1073446Notes

Reaction equation

HRID 1073446 reaction equation
C1(C[O:8][CH2:9][C@H:10]2[O:30][C@H:29]([C@@H:31]([CH2:40][O:41]CC3C=CC=CC=3)[O:32][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C@@H:20]([O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[C@@H:11]2[O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)C=CC=CC=1.B(F)(F)F.CCOCC>C(OC(=O)C)(=O)C>[C:14]1([CH2:13][O:12][C@H:11]2[C@H:20]([O:21][CH2:22][C:23]3[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=3)[C@@H:29]([C@@H:31]([CH2:40][OH:41])[O:32][CH2:33][C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[O:30][C@@H:10]2[CH2:9][OH:8])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

4

Reactant 2

HCID 8000Boron trifluoride etherateHCID 70360277HCID 70360277, compound

Product 1

HCID 70360326HCID 70360326, compound

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

In accordance with Flowchart D, 2,5-anhydro-D-mannose 26 is treated with acetyl chloride in methanol at reflux, then neutralized with lead carbonate, giving 2,5-anhydro-D-mannose, dimethyl acetal 27. which is treated with sodium hydride and benzyl bromide in dimethylformamide, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannose, dimethyl acetal 28. Compound 28 is then treated with tetrafluoroboric acid in acetonitrile, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannose 29 which is then treated with Tebbe's reagent in ether at -40° C., then neutralized with sodium hydroxide, giving 3,6-anhydro-1,2-dideoxy-4,5,7-tris-O-(phenylmethyl)-D-manno-hept-1-enitol 30. Compound 30 is treated with osmium tetroxide in pyridine, giving 2,5-anhydro-1,3,4-tris-O-(phenylmethyl)-D-glycero-D-manno-heptitol 31, which is treated with sodium hydride in dimethylformamide, followed by treatment with benzyl bromide, giving 2,5-anhydro-1,3,4,6,7-pentakis-O-(phenylmethyl)-D-glycero-D-manno-heptitol 32. Compound 32 is treated with borontrifluoride etherate in acetic anhydride, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)D-glycero-D-manno-heptitol, 1,7-diacetate 33, which is treated with sodium ethoxide in ethanol, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-glycero-D-manno-heptitol 34. Compound 34 is treated with diethyl phosphorochloridate in pyridine at reduced temperature, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-glycero-D-manno-heptitol, 1,7-bis(diethyl phosphate) 35. Substituting other esterifying agents as described in Flowchart A will result in the corresponding tetraesters. Compound 35 is treated with bromotrimethyl silane in chloroform at reduced temperature, under an inert atmosphere, giving 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-glycero-D-manno-heptitol, 1,7-bis(dihydrogen phosphate) 36, which is then hydrogenated over palladium on carbon in methanol, giving the product of Formula I, where R', R", R'" and R"" are hydrogen,

Sources & evidence

ORD record
ord-8726ee6ff9b04bf78dd66fa039b8f849
Source dataset
uspto-grants-1990_11
Patent number
US04968790

Reaction notes

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