Sulfuric Acid → HCID 70360444, compound

HRID 1073451Notes

Reaction equation

HRID 1073451 reaction equation
[OH:1][CH2:2][C@@:3]1([O:12][C@H:11]([CH2:13][OH:14])[C@@H:9]([OH:10])[C@@H:7]1[OH:8])[CH2:4][CH:5]=C.S(=O)(=O)(O)[OH:16].[BH4-].[Na+].P(Cl)(=O)(OC1C=CC=CC=1)OC1C=CC=CC=1>CC(C)=O.N1C=CC=CC=1.ClCCl.C(O)C.CO.C(O)(=O)C.[Pd].CO.S([O-])([O-])(=O)=O.[Cu+2].[Pt]=O>[OH:1][CH2:2][C@@:3]1([O:12][C@H:11]([CH2:13][OH:14])[C@@H:9]([OH:10])[C@@H:7]1[OH:8])[CH2:4][CH2:5][OH:16]

Participants

14

Reactant 4

HCID 1118Sulfuric AcidHCID 75654Diphenyl chlorophosphateHCID 4311764Sodium borohydrideHCID 70360289HCID 70360289, compound

Product 1

HCID 70360444HCID 70360444, compound

Reagents, catalysts & solvents 9

HCID 23938PalladiumCatalystHCID 24462Copper SulfateCatalystHCID 82844Platinum oxide (PtO)CatalystHCID 180AcetoneSolventHCID 702EthanolSolventHCID 887MethanolSolventHCID 1049PyridineSolvent2×HCID 6344DichloromethaneSolventHCID 10129899Acetic acid methanolSolvent

Procedure

In accordance with Flowchart H, D-fructofuranose, pentabenzoate and allyltrimethylsilane are reacted in acetonitrile at reduced temperature, in the presence of borontrifluoride etherate, giving 4,7-anhydro-4-C-[(benzoyloxy)methyl]-1,2,3-trideoxy-D-arabino-oct-1-enitol, 5,6,8-tribenzoate 56, which is reacted with sodium methoxide in methanol, giving 4,7-anhydro-1,2,3-trideoxy-4-C-(hydroxymethyl)-D-manno-oct-1-enitol 57. Compound 57 is reacted with copper sulfate and sulfuric acid in acetone, then neutralized giving 41,1,5:4,7-dianhydro-1,2,3-trideoxy-4-C-[(1-hydroxy-1-methylethoxy)methyl]-6,8-bis-O-(phenylmethyl)-D-manno-oct-1-enitol 58, which is first subjected to ozonolysis in a mixture of pyridine and dichloromethane and then reduced with sodium borohydride in ethanol, giving 3,6:31,4-dianhydro-2-deoxy-3-C-[(1-hydroxy-1-methylethoxy)methyl]-5,7-bis-O-(phenylmethyl)-D-manno-heptitol 59. Compound 59 is hydrogenated in methanol/acetic acid over palladium on carbon, giving 3,6:31,4-dianhydro-2-deoxy-3-C-[(1-hydroxy-1-methylethoxy)methyl]-D-manno-heptitol 60, which is reacted with diphenyl phosphorochloridate in pyridine at reduced temperature, giving the product 3,6:31,4-dianhydro-2-deoxy-3-C-[( 1-hydroxy-1-methylethoxy)methyl]-D-manno-heptitol, 1.7-bis-(diphenyl phosphate) 61, which is hydrogenated in methanol over platinum oxide, giving the product 3,6-anhydro-2-deoxy-3-C-(hydroxymethyl)-D-manno-heptitol, 1,7-bis(dihydrogen phosphate) 62. ##STR21##

Workup

  1. customneutralized giving 41,1,5
  2. customgiving 3,6
  3. customgiving 3,6
  4. customgiving the product 3,6

Sources & evidence

ORD record
ord-6fd0993b91ad433ca10338ddeffa8cdc
Source dataset
uspto-grants-1990_11
Patent number
US04968790

Reaction notes

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