Tetrabutylammonium Fluoride → tert-butyl N-[4-(cyclopropylsulfonylcarbamoyl)-18-hydroxy-2,15-dioxo-3,16-diazatricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamate

HRID 346969Notes

Reaction equation

HRID 346969 reaction equation
[C:1]([O:5][C:6](=[O:46])[NH:7][CH:8]1[C:26](=[O:27])[N:25]2[CH:21]([CH2:22][CH:23]([O:28][Si](C(C)(C)C)(C)C)[CH2:24]2)[C:20](=[O:36])[NH:19][C:18]2([C:37]([NH:39][S:40]([CH:43]3[CH2:45][CH2:44]3)(=[O:42])=[O:41])=[O:38])[CH:16]([CH2:17]2)[CH:15]=[CH:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1)([CH3:4])([CH3:3])[CH3:2].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[C:1]([O:5][C:6](=[O:46])[NH:7][CH:8]1[C:26](=[O:27])[N:25]2[CH:21]([CH2:22][CH:23]([OH:28])[CH2:24]2)[C:20](=[O:36])[NH:19][C:18]2([C:37]([NH:39][S:40]([CH:43]3[CH2:45][CH2:44]3)(=[O:41])=[O:42])=[O:38])[CH:16]([CH2:17]2)[CH:15]=[CH:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1)([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 66915233[18-(Tert-butyl-dimethyl-silanyloxy)-4-cyclopropanesulfonylaminocarbonyl-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]-carbamic acid tert-butyl ester

Product 1

HCID 68797769tert-butyl N-[4-(cyclopropylsulfonylcarbamoyl)-18-hydroxy-2,15-dioxo-3,16-diazatricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamateYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of [18-(tert-butyl-dimethylsilanyloxy)-4-cyclopropanesulfonylaminocarbonyl-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]-carbamic acid tert-butyl ester (330 mg, 0.48 mmoL) in 25 mL of THF was added tetrabutylammonium fluoride (150 mg, 0.54 mmoL). The reaction mixture was stirred at rt for 18 h, and then the THF was removed by rotary evaporation. The residue was partitioned between ethyl acetate and water. The organic phase was dried (MgSO4) and concentrated in vacuo to give the crude product. It was then purified by triturating with hexane to yield 200 mg (73%) of (4-cyclopropanesulfonylaminocarbonyl-18-hydroxy-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl)-carbamic acid tert-butyl ester as a white solid. 1H NMR (500 MHz, CD3Cl) δ 1.87–1.64 (m, 21H), 1.70–1.98 (m, 3H), 2.15–2.56 (m, 5H), 2.85–2.94 (m, 1H), 3.71 (d, J=13.91 Hz, 1H), 4.10–4.26 (m, 2H), 4.51 (t, J=7.87 Hz, 1H), 4.62 (s, 1H), 4.98 (m, 1H), 5.06 (d, J=8.78 Hz, 1H), 5.64–5.71 (m, 1H), 6.72 (s, 1H), 10.24 (s, 1H). LC-MS (Method A, retention time: 2.85 min), MS m/z 569 (M++1).

Workup

  1. customthe THF was removed by rotary evaporation
  2. customThe residue was partitioned between ethyl acetate and water
  3. dry with materialThe organic phase was dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customto give the crude product
  6. customIt was then purified
  7. customby triturating with hexane

Sources & evidence

ORD record
ord-c0188ebad1194acdafff8f296cefbf12
Source dataset
uspto-grants-2007_02
Patent number
US07173004B2

Reaction notes

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