Benzyl Alcohol → Trans 2-benzyloxycarbonylamino-3-carboethoxy-1,2,3,4-tetrahydronaphthalene

HRID 901993Notes

Reaction equation

HRID 901993 reaction equation
[C:1]([C@H:6]1[C@H:15](C(O)=O)[CH2:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH2:7]1)([O:3][CH2:4][CH3:5])=[O:2].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:26])C=CC=CC=1.C([N:38]([CH2:41]C)CC)C.[CH2:43]([OH:50])[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1>C1(C)C=CC=CC=1.C(OCC)(=O)C.[Cl-].[NH4+]>[CH2:43]([O:50][C:41]([NH:38][C@H:15]1[C@H:6]([C:1]([O:3][CH2:4][CH3:5])=[O:2])[CH2:7][C:8]2[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH2:14]1)=[O:26])[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1

Participants

8

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 58646746Trans 2-carboethoxy-3-carboxy-1,2,3,4-tetrahydronaphthalene

Product 1

HCID 58646750Trans 2-benzyloxycarbonylamino-3-carboethoxy-1,2,3,4-tetrahydronaphthalene

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of trans 2-carboethoxy-3-carboxy-1,2,3,4-tetrahydronaphthalene (546 mg, 2.2 mmol) in toluene (15 mL) under nitrogen was added diphenylphosphoryl azide (0.62 mL, 2.86 mmol), triethylamine (0.4 mL, 2.86 mmol) and benzyl alcohol (1.14 mL, 11 mmol). The reaction mixture was heated to 100° C. for 19 h. The toluene was removed under vacuum to yield a residue. The residue was diluted with ethyl acetate and aqueous ammonium chloride solution. The organic layer was washed with 1.0 M aqueous hydrochloric acid solution, saturated aqueous sodium carbonate solution and brine, dried over anhydrous magnesium sulfate, and concentrated under vacuum to yield a residue. The residue was purified by silica gel chromatography (10% ethyl acetate in hexane was used) to obtain the title compound (800 mg, containing some benzyl alcohol). 13C NMR (500 MHz, CDCl3) δ 173.2, 155.5, 136.3, 133.5, 133.2, 129.0, 128.5, 128.1, 127.6, 126.9, 126.4, 126.3, 66.7, 65.3, 48.7, 45.3, 35.0, 30.4, 14.1. 1H NMR (400 MHz, CDCl3) δ 7.02-7.38 (m, 9H), 5.10 (s, 2H), 4.29 (m, 1H), 4.14 (m, 2H), 3.22 (m, 2H), 3.02 (dd, J=5.7, 17.2 Hz, 1H), 2.88 (m, 1H), 2.76 (dd, J=7.2, 16.8 Hz, 1H), 1.23 (t, J=7.0 Hz, 3H).

Workup

  1. customThe toluene was removed under vacuum
  2. customto yield a residue
  3. washThe organic layer was washed with 1.0 M aqueous hydrochloric acid solution, saturated aqueous sodium carbonate solution and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under vacuum
  6. customto yield a residue
  7. customThe residue was purified by silica gel chromatography (10% ethyl acetate in hexane was used)

Sources & evidence

ORD record
ord-2b54ac2ac3234f01a1dd52de41150b0f
Source dataset
uspto-grants-2008_04
Patent number
US07365061B2

Reaction notes

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