Triphenylphosphine → Di-tert-butyl bicarbamate

HRID 1797126Notes

Reaction equation

HRID 1797126 reaction equation
C1(C(C2C=CC=CC=2)CNC(=O)[C@H](NS(C2C=CC=CC=2[N+]([O-])=O)(=O)=O)CC2C=CC=CC=2)C=CC=CC=1.C(N1C=C(CCO)N=C1)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N:85]([C:94]([O:96][C:97]([CH3:100])([CH3:99])[CH3:98])=[O:95])=[N:86][C:87]([O:89][C:90]([CH3:93])([CH3:92])[CH3:91])=[O:88]>C(Cl)Cl>[NH:85]([C:94]([O:96][C:97]([CH3:100])([CH3:99])[CH3:98])=[O:95])[NH:86][C:87]([O:89][C:90]([CH3:91])([CH3:92])[CH3:93])=[O:88]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 97268Di-tert-butyl azodicarboxylateHCID 106894902-(1-Trityl-1H-imidazol-4-yl)ethanolHCID 69588746HCID 69588746, compound

Product 1

HCID 85431Di-tert-butyl bicarbamate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of the product of step 2 (3.40 g, 6.42 mmol) and 2-(1-trityl-1H-imidazol-4-yl)-ethanol (2.73 g, 7.70 mmol) in methylene chloride (40 mL) was added triphenylphosphine (2.19 g, 8.35 mmol) followed by di-tert-butyl azodicarboxylate (1.77 g, 7.69 mmol). After 3 hours the reaction was concentrated and the residue partitioned between ethyl acetate and aqueous sodium bicarbonate solution. The organic layer was dried (sodium sulfate) and concentrated to yield an amber gum. Flash chromatography over silica (methylene chloride/methanol) afforded 5.42 g (97%) of partially purified product (contaminated with di-tert-butyl hydrazodiformate) as a pale yellow foam: 1H NMR (CDCl3) δ 7.81–7.74 (m, 1H), 7.64–7.55 (m, 1H), 7.53–7.44 (m, 2H), 7.41–7.03 (m, 31H), 6.69 (t, J=5.6, 1H), 6.53 (s, 1H), 4.48 (t, J=8.1, 1H), 4.08 (t, J=8.1, 1H), 3.84–3.58 (m, 4H), 3.44–3.34 (m, 1H), 2.91–3.80 (m, 1H), 2.78–2.68 (m, 1H), 2.63–2.51 (m, 1H) ppm.

Workup

  1. concentrationAfter 3 hours the reaction was concentrated
  2. customthe residue partitioned between ethyl acetate and aqueous sodium bicarbonate solution
  3. dry with materialThe organic layer was dried (sodium sulfate)
  4. concentrationconcentrated
  5. customto yield an amber gum

Sources & evidence

ORD record
ord-13cea7162dba442982a7bd203226902e
Source dataset
uspto-grants-2006_04
Patent number
US07034031B2

Reaction notes

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