Isobutylene → 1,5-Bis(tert-butoxycarbonyl)-2-formyl-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridine

HRID 352871Notes

Reaction equation

HRID 352871 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:16]2[CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12][C:11]=2[CH:10]=[C:9]1[CH2:24][OH:25])=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.S([O-])([O-])(=O)=S.[Na+].[Na+].C(=O)(O)[O-].[Na+].C=C(C)C>C(Cl)Cl.C(OCC)(=O)C>[C:1]([O:5][C:6]([N:8]1[C:16]2[CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12][C:11]=2[CH:10]=[C:9]1[CH:24]=[O:25])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 5

HCID 8255IsobutyleneHCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 113487371,5-bis(t-butoxycarbonyl)-2-hydroxymethyl-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridine

Product 1

HCID 111522941,5-Bis(tert-butoxycarbonyl)-2-formyl-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridine

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1,5-bis(t-butoxycarbonyl)-2-hydroxymethyl-4,5,6,7-tetrahydro-1H-pyrrolo[3,2-c]pyridine (14.0 mg) in methylene chloride (2.0 ml), Dess-Martin periodinane (34.0 mg) was added at room temperature. The resulting mixture was stirred for 1 hour. To the reaction mixture, ethyl acetate (10 ml), a 10% aqueous solution (10 ml) of sodium thiosulfate and an aqueous solution (10 ml) of sodium bicarbonate were added to cause separation. The water layer was extracted with ethyl acetate (10 ml). The organic layers were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue thus obtained was purified by thin-layer preparative chromatography on silica gel (hexane:ethyl acetate=2:1), whereby the title compound (9.8 mg) was obtained as a colorless transparent caramel-like substance. IR(KBr)cm−1: 2976, 2933, 1741, 1697, 1660, 1479, 1413, 1367, 1346, 1298, 1281, 1234, 1165, 1146, 1103, 895, 850, 768. 1H-NMR (CDCl3) δ: 1.48(9H,s), 1.63(9H,s), 2.96(2H,br t,J=5.4 Hz), 3.68(2H,br t,J=5.4 Hz), 4.37(2H,s), 6.97(1H,s), 10.14(1H,br s). MS (FAB/m-NBA) m/z: 351 [(M+H)+], 295 [(M+H-isobutene(56))+], 239 [(M+H)—2×isobutene (56))+].

Workup

  1. customseparation
  2. extractionThe water layer was extracted with ethyl acetate (10 ml)
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue thus obtained
  6. customwas purified by thin-layer preparative chromatography on silica gel (hexane:ethyl acetate=2:1), whereby the title compound (9.8 mg)
  7. customwas obtained as a colorless transparent caramel-like substance

Sources & evidence

ORD record
ord-c4ac53ca315341719fc4a27dbc0ba90a
Source dataset
uspto-grants-2004_06
Patent number
US06747023B1

Reaction notes

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