Tetrabutylammonium Fluoride → tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-hydroxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamate

HRID 708990Notes

Reaction equation

HRID 708990 reaction equation
[C:1]([O:5][C:6]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([CH2:25][C:26]2[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH:29]=[CH:28][CH:27]=2)[C@@H:20]([O:36][Si](C(C)C)(C(C)C)C(C)C)[C@H:19]([CH3:47])[O:18][C:17]1=[O:48])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1.[Na+].[Cl-]>[C:11]([O:10][C:9]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([CH2:25][C:26]2[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH:29]=[CH:28][CH:27]=2)[C@@H:20]([OH:36])[C@H:19]([CH3:47])[O:18][C:17]1=[O:48])[C:6](=[O:7])[O:5][C:1]([CH3:3])([CH3:4])[CH3:2])=[O:15])([CH3:12])([CH3:13])[CH3:14]

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 123241785HCID 123241785, compound

Product 1

HCID 117974424tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-hydroxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamateYield 72%

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-9-methyl-7-(1-naphthylmethyl)-2-oxo-8-triisopropylsilyloxy-1,5-dioxonan-3-yl]carbamate (2.54 g, 3.70 mmol) in THF (18.5 ml) was added TBAF (1.94 g, 7.41 mmol, 1M in THF) at room temperature. The reaction was stirred for 3.5 h, diluted with a 1/2 sat. aqueous NaCl solution (10 mL), and extracted with EtOAc (3×10 mL). The combined extracts were dried over Na2SO4, filtered, and concentrated to dryness under reduced pressure. The resulting clear oil was purified by flash chromatography (SiO2, 0→50% acetone/hexanes) to afford tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-hydroxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamate (1.41 g, 72%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J=8.5, 1.4 Hz, 1H), 7.87-7.79 (m, 1H), 7.72 (d, J=8.1 Hz, 1H), 7.54-7.41 (m, 2H), 7.42-7.27 (m, 2H), 5.19 (dd, J=8.8, 5.7 Hz, 1H), 5.00-4.88 (m, 1H), 4.10 (dd, J=11.9, 5.8 Hz, 1H), 3.89 (dd, J=12.0, 8.7 Hz, 1H), 3.68-3.51 (m, 4H), 2.79 (t, J=12.2 Hz, 1H), 2.58-2.51 (m, 1H), 2.15 (q, J=8.7, 7.4 Hz, 1H), 1.51 (d, J=6.4 Hz, 3H), 1.46 (s, 18H); 13C NMR (101 MHz, CDCl3) δ 169.95, 152.69, 135.84, 134.02, 132.04, 128.77, 127.46, 127.16, 126.03, 125.56, 125.25, 124.04, 83.17, 77.69, 76.26, 73.23, 70.87, 57.38, 46.90, 33.38, 27.92, 18.67; ESIMS m/z 553 ([M+Na]+).

Workup

  1. extractionextracted with EtOAc (3×10 mL)
  2. dry with materialThe combined extracts were dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated to dryness under reduced pressure
  5. customThe resulting clear oil was purified by flash chromatography (SiO2, 0→50% acetone/hexanes)

Sources & evidence

ORD record
ord-27ca4e343ef34b2f9f7a52435dc8df4a
Source dataset
uspto-grants-2015_11
Patent number
US09179674B2

Reaction notes

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