Triphenylphosphine → Benzyl (S)-2-(8,9-dihydro-9-methyl-7H-[1,4]oxazino[2,3-g]indazol-1-yl)-1-methylethylcarbamate

HRID 915747Notes

Reaction equation

HRID 915747 reaction equation
O[C:2]1[C:10]([N:11]([CH2:13][CH2:14][OH:15])[CH3:12])=[C:9]2[C:5]([CH:6]=[N:7][N:8]2[CH2:16][C@@H:17]([NH:19][C:20](=[O:29])[O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH3:18])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[Cl-].[NH4+]>O1CCCC1>[CH3:12][N:11]1[C:10]2[C:2](=[CH:3][CH:4]=[C:5]3[C:9]=2[N:8]([CH2:16][C@@H:17]([NH:19][C:20](=[O:29])[O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH3:18])[N:7]=[CH:6]3)[O:15][CH2:14][CH2:13]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 136375621Benzyl (S)-2-[6-hydroxy-7-[(2-hydroxyethyl)methylamino]-1H-indazol-1-yl]-1-methylethylcarbamate

Product 1

HCID 86598606Benzyl (S)-2-(8,9-dihydro-9-methyl-7H-[1,4]oxazino[2,3-g]indazol-1-yl)-1-methylethylcarbamateYield 89.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of the product from Step B (0.36 g, 0.82 mmol) in tetrahydrofuran (10 mL) at 0° C. was added triphenylphospine (0.26 g, 0.98 mmol) followed by diethyl azodicarboxylate (0.23 mL, 1.23 mmol). After 2 h, a saturated aqueous solution of ammonium chloride (30 mL) was added and the mixture was extracted with ethyl acetate (3×65 mL). The combined extracts were washed with brine (10 mL), dried (MgSO4), and evaporated to a residue which was purified by chromatography (silica, 30%-50% ethyl acetate in hexane) to give an oil (0.28 g, 89%): 1H NMR (CDCl3) δ 7.88 (1H, s), 7.30 (6H, m), 6.73 (1H, d, J=8.4 Hz), 4.91 (2H, s), 4.63 (2H, m), 4.37 (2H, m), 4.09 (1H, m), 3.26 (2H, m), 2.73 (3H, s), 1.06 (3H, d, J=6.4 Hz); MS (ES) m/z 381 (M+).

Workup

  1. extractionthe mixture was extracted with ethyl acetate (3×65 mL)
  2. washThe combined extracts were washed with brine (10 mL)
  3. dry with materialdried (MgSO4)
  4. customevaporated to a residue which
  5. customwas purified by chromatography (silica, 30%-50% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-a704288189a24c0b8b2e55eef403f376
Source dataset
uspto-grants-2007_09
Patent number
US07268131B2

Reaction notes

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