Triphenylphosphine → Di-tert-butyl 1-(cyclopropylmethyl)hydrazine-1,2-dicarboxylate

HRID 2064498Notes

Reaction equation

HRID 2064498 reaction equation
[CH:1]1([CH2:4]O)[CH2:3][CH2:2]1.[NH:6]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O>C1COCC1>[CH:1]1([CH2:4][N:6]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH:7][C:8]([O:10][C:11]([CH3:12])([CH3:13])[CH3:14])=[O:9])[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75644CyclopropanemethanolHCID 85431Di-tert-butyl bicarbamateHCID 97268Di-tert-butyl azodicarboxylate

Product 1

HCID 66643119Di-tert-butyl 1-(cyclopropylmethyl)hydrazine-1,2-dicarboxylateYield 354.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of cyclopropylmethanol (7.15 ml, 90 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.30 g, 27.1 mmol) and triphenylphosphine (28.5 g, 109 mmol) in THF (100 mL) was added di-tert-butyl azodicarboxylate (25 g, 109 mmol) portion wise at ambient temperature. The mixture was stirred for 2 hours then concentrated. Solid triphenylphosphineoxide was removed by filtration. The filtrate was concentrated and the residue was purified by flash chromatography (silica gel, eluted with a gradient of 5-25% EtOAc in hexane) to provide 27.5 g (96%) of title compound. 1H NMR (300 MHz, CDCl3) δ ppm 0.15-0.26 (m, 2H), 0.42-0.54 (m, 2H), 0.91-1.09 (m, 1H), 1.47 (s, 9H), 1.48 (s, 9H), 3.31 (d, J=6.10 Hz, 2H), 6.38 (s, 1H).

Workup

  1. concentrationthen concentrated
  2. customSolid triphenylphosphineoxide was removed by filtration
  3. concentrationThe filtrate was concentrated
  4. customthe residue was purified by flash chromatography (silica gel
  5. washeluted with a gradient of 5-25% EtOAc in hexane)

Sources & evidence

ORD record
ord-77ab10bee8a34641b762f8c41cb5f93f
Source dataset
uspto-grants-2012_10
Patent number
US08288428B2

Reaction notes

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