Hydrochloric Acid → HCID 67495039, compound

HRID 1044799Notes

Reaction equation

HRID 1044799 reaction equation
N#N.C(OC(=O)[NH:9][C@@H:10]1[CH2:15][CH2:14][C@@H:13]([CH2:16]O)[O:12][CH2:11]1)(C)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N1C=CN=C1.II.[NH:45]1[CH2:49][CH2:48][CH2:47][CH2:46]1.C([O-])([O-])=O.[K+].[K+].[ClH:56]>C(Cl)Cl.CC(=O)OCC.CC(C)=O.CO>[ClH:56].[N:45]1([CH2:16][C@H:13]2[O:12][CH2:11][C@H:10]([NH2:9])[CH2:15][CH2:14]2)[CH2:49][CH2:48][CH2:47][CH2:46]1

Participants

11

Reactant 8

HCID 313Hydrochloric AcidHCID 795ImidazoleHCID 807IodineHCID 947NitrogenHCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 109880991,5-Anhydro-2,3,4-trideoxy-2-[[(1,1-diMethylethoxy)carbonyl]aMino]-D-erythrohexitol

Product 1

HCID 67495039HCID 67495039, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 18970191HCID 18970191, compoundSolvent

Procedure

In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), to an ice-cold solution of (3R,6S)-6-hydroxymethyl-tetrahydro-2H-pyran-3-yl carbamic acid tert-butyl ester (328 mg, 1.40 mmol, H. S. Overkleeft et al. Eur. J. Org. Chem. 2003, 2418), triphenylphoshine on polystyrene (6.16 mmol) and imidazole (203 mg, 2.95 mmol) in dry CH2Cl2 (14 mL) was added iodine (891 mg, 3.48 mmol). The reaction mixture was warmed to rt and stirred at this temperature until completion of the reaction. The mixture was then filtered, CH2Cl2 removed under reduced pressure. The residue was redissolved in EA, successively washed with 10% aq. Na2SO3 and brine, dried over Na2SO4, filtered and concentrated under reduced pressure. After purification by FC, the iodide was redissolved in CH3CN (15 mL) and treated with pyrrolidine (1.13 mL, 13.57 mmol) and K2CO3 (750 mg, 5.43 mmol). The reaction mixture was stirred at 85° C. until completion of the reaction, filtered and concentrated under reduced pressure. The amine was purified by FC (hept-EA-acetone, 1:0:0->0:0:1) and then the Boc group was removed by treatment with HCl (4.0 M in dioxane, 9 eq.) in dry CH2Cl2 (2 mL). The title compound was obtained after trituration in hot EA/acetone/MeOH as an off-white solid. LC-MS-conditions 01: tR=0.15 min; [M+H]+=185.06.

Workup

  1. filtrationThe mixture was then filtered
  2. customCH2Cl2 removed under reduced pressure
  3. dissolutionThe residue was redissolved in EA
  4. washsuccessively washed with 10% aq. Na2SO3 and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customAfter purification by FC
  9. dissolutionthe iodide was redissolved in CH3CN (15 mL)
  10. stirringThe reaction mixture was stirred at 85° C. until completion of the reaction
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure
  13. customThe amine was purified by FC (hept-EA-acetone, 1:0:0->0:0:1)

Sources & evidence

ORD record
ord-4bb1cd71baac4cbbb87288f2d376c59c
Source dataset
uspto-grants-2013_10
Patent number
US08563714B2

Reaction notes

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