Triphenylphosphine → HCID 70079702, compound

HRID 264343Notes

Reaction equation

HRID 264343 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH2:11][CH2:12][C@@H:13]2[O:18][C:17](=[O:19])[CH2:16][C@@H:15]([CH:20]=[CH2:21])[CH2:14]2)=[CH:5][CH:4]=1)#[N:2].[OH-].[Na+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.N(C(OCC)=O)=NC(OCC)=O>CO.C1COCC1.O.C1COCC1.CCOC(C)=O.CCCCCC>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH2:11][CH2:12][C@H:13]2[O:18][C:17](=[O:19])[CH2:16][C@@H:15]([CH:20]=[CH2:21])[CH2:14]2)=[CH:5][CH:4]=1)#[N:2]

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 70081111HCID 70081111, compound

Product 1

HCID 70079702HCID 70079702, compoundYield 69%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 21226206Ethyl acetate hexaneSolventHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of the product of step B (1.52 g, 5.47 mmol) in 15 mL of MeOH:THF (2:1) was added 1H NaOH (5.9 mL, 5.9 mmol) and the reaction stirred at room temperature for 1.5 hours. The reaction was diluted with water and washed with Et2O. The aqueous phase was acidified with 1H NaHSO4, extracted with EtOAc, dried (MgSO4), filtered and evaporated under reduced pressure. The residue and Ph3P (1.86 g, 7.11 mmol) was immediately dissolved in dry THF (20 mL) and cooled to -40° C. Neat diethyl azodicarboxylate (1.27 g, 7.42 mmol) was added dropwise via syringe and the solution stirred at -40° C. for 3 hours. Concentration of the solvent under reduced pressure and silica gel chromatography (EtOAc:hexane 4:6) of the residue afforded 1.05 g (69%) of the title product as a colorless oil. NMR spectrum analysis indicated the product was contaminated with ~10% of the trans isomer. 1H-NMR (300 MHz, CDCl3) δ1.25-1.80 (m, 7H), 1.90-2.00 (m, 1H), 2.24 (dd, J=11 Hz, J=17 Hz, 1H), 2.55-2.79 (m, 4H), 4.30 (m, 1H) 5.02-5.14 (m, 2H), 5.66-5.80 (m, 1H), 7.27 (d, J=8 Hz, 2H), 7.57 (d, J=8 Hz, 2H).

Workup

  1. washwashed with Et2O
  2. extractionextracted with EtOAc
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. temperaturecooled to -40° C
  7. stirringthe solution stirred at -40° C. for 3 hours

Sources & evidence

ORD record
ord-6e24ebeeacd440368870b9a03e8475b4
Source dataset
uspto-grants-1997_07
Patent number
US05646183

Reaction notes

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