Triphenylphosphine → trans-3-Azido-proline

HRID 415873Notes

Reaction equation

HRID 415873 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.C[O:16][C:17](=[O:24])[C@@H:18]1[C@H:22](O)[CH2:21][CH2:20][NH:19]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P([N:58]=[N+:59]=[N-:60])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1>[N:58]([C@H:22]1[CH2:21][CH2:20][NH:19][C@@H:18]1[C:17]([OH:16])=[O:24])=[N+:59]=[N-:60]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 199401P,P-Diphenylphosphinic azideHCID 5363146Diisopropyl azodicarboxylateHCID 45082777Methyl (3R)-3-hydroxy-L-prolinate

Product 1

HCID 86638431trans-3-Azido-proline

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

DIAD (23.88 mmol, 1.3 eq.) was added dropwise with stirring to a solution of cis-3-hydroxyproline methyl ester# (18.36 mmol, 1 eq.) and triphenylphosphine (22.9 mmol, 1.25 eq.) in THF (100 mL) at 0° C. Then a solution of diphenylphosphoryl azide (22.9 mmol, 1.25 eq.) in THF (20 ml) was added. The reaction was slowly warmed to rt and stirred for 16 h. The solvent was then removed under vacuum, and the residue triturated with cold ether to remove triphenylphosphine oxide. Upon filtration, the filtrate was concentrated and subjected to column chromatography (SiO2, gradient 15%-20% ethyl acetate/hexanes) to give the desired trans-3-azido-proline compound.

Workup

  1. customThe solvent was then removed under vacuum
  2. customthe residue triturated with cold ether
  3. customto remove triphenylphosphine oxide
  4. filtrationUpon filtration
  5. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-85db65d356ef4e7cb1c64bcc0b991139
Source dataset
uspto-grants-2012_01
Patent number
US08088804B2

Reaction notes

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