Tetrabutylammonium Fluoride → HCID 59135184, compound

HRID 1028610Notes

Reaction equation

HRID 1028610 reaction equation
[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[Si]([O:26][C@H:27]([C:41]1[N:45]([CH3:46])[N:44]=[N:43][N:42]=1)[C@@H:28]([NH:30][C:31](=[O:40])[O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH3:29])(C(C)(C)C)(C)C.[Si]([O:54][C@H:55]([C:69]1[N:70]=[N:71][N:72]([CH3:74])[N:73]=1)[C@@H:56]([NH:58][C:59](=[O:68])[O:60][CH2:61][C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=1)[CH3:57])(C(C)(C)C)(C)C>C1COCC1.[NH4+].[Cl-]>[OH:54][C@H:55]([C:69]1[N:70]=[N:71][N:72]([CH3:74])[N:73]=1)[C@@H:56]([NH:58][C:59](=[O:68])[O:60][CH2:61][C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=1)[CH3:57].[OH:26][C@H:27]([C:41]1[N:45]([CH3:46])[N:44]=[N:43][N:42]=1)[C@@H:28]([NH:30][C:31](=[O:40])[O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH3:29]

Participants

7

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 86603426HCID 86603426, compoundHCID 86603427HCID 86603427, compound

Product 2

HCID 59135184HCID 59135184, compoundHCID 59135198HCID 59135198, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
0 °C

Procedure

Tetrabutylammonium fluoride (1M, in THF, 177 μL, 0.177 mmol) was added dropwise to a stirred solution of benzyl [(1S,2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-methyl-2-(1-methyl-1H-tetrazol-5-yl)ethyl]carbamate and benzyl [(1S,2S)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-methyl-2-(2-methyl-2H-tetrazol-5-yl)ethyl]carbamate (2:1 mixture of regioisomers, 65.2 mg, 0.161 mmol) in THF (2 mL) at 0° C. The reaction was stirred for 2 h at 0° C., diluted with saturated NH4Cl (10 mL) and extracted with EtOAc (3×30 mL). The combined extracts were dried (Na2SO4) and concentrated in vacuo to give the crude product. This was purified by flash chromatography (Si, 12×160 mm, 0-80% EtOAc in hexanes gradient) to afford benzyl [(1S,2S)-2-hydroxy-1-methyl-2-(2-methyl-2H-tetrazol-5-yl)ethyl]carbamate and benzyl [(1S,2S)-2-hydroxy-1-methyl-2-(1-methyl-1H-tetrazol-5-yl)ethyl]carbamate. 2-methyl isomer (INTERMEDIATE 20): LCMS calc.=292.1; found=292.1 (M+1)+. 1H NMR (500 MHz, CDCl3) δ 7.33-7.29 (m, 5H), 5.59 (d, J=8.5 Hz, 1H), 5.09-5.00 (m, 5H), 4.49 (m, 1H), 4.26 (s, 3H), 1.07 (d, J=6.9 Hz, 3H). 1-methyl isomer (INTERMEDIATE 19): LCMS calc.=292.1; found=292.1 (M+1)+. 1H NMR (500 MHz, CDCl3) δ 7.33-7.29 (m, 5H), 5.72 (s, 1H), 5.07 (m, 3H), 4.99 (m, 2H), 4.18 (m, 1H), 4.10 (s, 3H), 1.24 (d, J=6.7 Hz, 3H).

Workup

  1. extractionextracted with EtOAc (3×30 mL)
  2. dry with materialThe combined extracts were dried (Na2SO4)
  3. concentrationconcentrated in vacuo
  4. customto give the crude product
  5. customThis was purified by flash chromatography (Si, 12×160 mm, 0-80% EtOAc in hexanes gradient)

Sources & evidence

ORD record
ord-4ea37f3e125c470e88856313531ed93c
Source dataset
uspto-grants-2014_05
Patent number
US08735435B2

Reaction notes

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