Triphenylphosphine → HCID 117871161, compound

HRID 530621Notes

Reaction equation

HRID 530621 reaction equation
[C:1]([O:5][C:6](=[O:23])[N:7]([CH2:20][CH2:21][OH:22])[CH2:8][CH:9](O)[C:10]1[CH:15]=[CH:14][N:13]=[C:12]([CH:16]([CH3:18])[CH3:17])[N:11]=1)([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>COC(C)(C)C>[C:1]([O:5][C:6]([N:7]1[CH2:20][CH2:21][O:22][CH:9]([C:10]2[CH:15]=[CH:14][N:13]=[C:12]([CH:16]([CH3:18])[CH3:17])[N:11]=2)[CH2:8]1)=[O:23])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 117870297HCID 117870297, compound

Product 1

HCID 117871161HCID 117871161, compoundYield 68.3%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

(2-Hydroxyethyl)-[2-hydroxy-2-(2-isopropyl-pyrimidin-4-yl)-ethyl]-carbamic acid tert-butyl ester (396 mg, 1.22 mmol) was dissolved in methyl-t-butylether (MTBE) (15 ml). Triphenylphosphine (383 mg, 1.46 mmol) was added. To this mixture was added diisopropyl azodicarboxylate (295 mg, 288 μl, 1.46 mmol) dropwise. The solution was stirred at room temperature overnight. A white solid was filtered off, washed with MTBE (2×10 mL). The combined filtrate and washes were concentrated and the resulting residue was purified by Analogix flash column chromatography (40 g silica gel, 0% to 20% ethyl acetate in hexanes gradient) to afford 2-(2-isopropyl-pyrimidin-4-yl)-morpholine-4-carboxylic acid tert-butyl ester (256 mg) as a white solid. (M+H)|=308 m/e. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.35 (d, J=6.82 Hz, 6H) 1.52 (s, 9H) 2.80 (br. s., 1H) 3.06 (d, J=10.61 Hz, 1H) 3.22 (dt, J=13.71, 6.92 Hz, 1H) 3.72 (td, J=11.62, 2.53 Hz, 1H) 3.98 (br. s., 1H) 4.07 (d, J=9.60 Hz, 1H) 4.48 (dd, J=10.48, 2.15 Hz, 2H) 7.31 (d, J=5.05 Hz, 1H) 8.69 (d, J=5.05 Hz, 1H).

Workup

  1. filtrationA white solid was filtered off
  2. washwashed with MTBE (2×10 mL)
  3. concentrationThe combined filtrate and washes were concentrated
  4. customthe resulting residue was purified by Analogix flash column chromatography (40 g silica gel, 0% to 20% ethyl acetate in hexanes gradient)

Sources & evidence

ORD record
ord-bd97afb20d1e4670b38faac76f8e6adf
Source dataset
uspto-grants-2016_05
Patent number
US09353096B2

Reaction notes

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