Triphenylphosphine → Tert-butyl (1s,2r)-1-benzyl-2-hydroxyhexylcarbamate

HRID 1987149Notes

Reaction equation

HRID 1987149 reaction equation
[CH2:1]([C@H:8]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[C@H:9]([OH:14])[CH2:10][CH2:11][CH2:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:42]=[N+:43]=[N-:44].CCOC(/N=N/C(OCC)=O)=O>C1COCC1>[CH2:1]([C@H:8]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[C@H:9]([OH:14])[CH2:10][CH2:11][CH2:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N:42]([C@@H:9]([CH2:10][CH2:11][CH2:12][CH3:13])[C@@H:8]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[N+:43]=[N-:44]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 24530Hydrazoic acidHCID 5462977Diethyl azodicarboxylateHCID 90726167Tert-butyl (1s,2r)-1-benzyl-2-hydroxyhexylcarbamate2×

Product 2

HCID 90726167Tert-butyl (1s,2r)-1-benzyl-2-hydroxyhexylcarbamateHCID 90893745HCID 90893745, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of tert-butyl (1S,2R)-1-benzyl-2-hydroxyhexylcarbamate (1.24 g, 4.03 mmol), triphenylphosphine (1.06 g, 4.03 mmol) in 40 mL THF was added hydrozoic acid HN3 (4 mL, 8.07 mmol, 2M in benzene) followed by dropwise addition of diethylazodicarboxylate (0.7 mL, 4.44 mmol) in 10 mL THF. The reaction mixture was stirred at room temperature for 8 h, combined with a previous 250 mg tert-butyl (1S,2R)-1-benzyl-2-hydroxyhexylcarbamate probe reaction, concentrated in vacuo, and purified by flash chromatography (120 g silica, 0−>50% EtOAc/hexanes) to afford tert-butyl (1S,2R)-1-benzyl-2-hydroxyhexylcarbamate and tert-butyl (1S,2S)-2-azido-1-benzylhexylcarbamate as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.36-7.16 (m, 5H), 4.63 (d, J=10.1 Hz, 1H), 4.00-3.88 (m, 1H), 3.40-3.28 (m, 1H), 2.91 (A of ABX, dd, J=13.6, 6.8 Hz, 1H), 2.76 (B of ABX, dd, J=13.6, 9.1 Hz, 1H), 1.70-1.48 (m, 2H), 1.42-1.20 (m, 4H), 1.39 (s, 9H), 0.52 (t, J=7.1 Hz, 3H).

Workup

  1. concentrationconcentrated in vacuo
  2. custompurified by flash chromatography (120 g silica, 0−>50% EtOAc/hexanes)

Sources & evidence

ORD record
ord-0e10ce1cc14448a78eb05a602bc161b8
Source dataset
uspto-grants-2009_06
Patent number
US07550481B2

Reaction notes

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