Tetrabutylammonium Fluoride → (R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-N-((3S,6R)-6-hydroxy-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl)-2-methoxy-acetamide

HRID 2224022Notes

Reaction equation

HRID 2224022 reaction equation
C([Si](C)(C)[O:6][C@H:7]1[CH2:13][N:12]([CH2:14][C:15]2[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=2)[C:11](=[O:21])[C@@H:10]([NH:22][C:23](=[O:42])[C@@H:24]([C@H:27]2[C@H:32]([OH:33])[C@@H:31](/[CH:34]=[CH:35]/[C:36]([CH3:39])([CH3:38])[CH3:37])[O:30][C:29]([CH3:41])([CH3:40])[O:28]2)[O:25][CH3:26])[CH2:9][CH2:8]1)(C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>>[CH3:37][C:36]([CH3:39])([CH3:38])/[CH:35]=[CH:34]/[C@H:31]1[O:30][C:29]([CH3:40])([CH3:41])[O:28][C@@H:27]([C@@H:24]([O:25][CH3:26])[C:23]([NH:22][C@H:10]2[CH2:9][CH2:8][C@@H:7]([OH:6])[CH2:13][N:12]([CH2:14][C:15]3[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=3)[C:11]2=[O:21])=[O:42])[C@@H:32]1[OH:33]

Participants

3

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 69266828(R)-N-[(3S,6R)-6-(tert-butyl-dimethyl-silanyloxy)2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl]-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetamide

Product 1

HCID 69266165(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-N-((3S,6R)-6-hydroxy-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl)-2-methoxy-acetamideYield 75.2%

Procedure

To a stirred solution of (R)-N-[(3S,6R)-6-(tert-butyl-dimethyl-silanyloxy)-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl]-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetamide (1.2 g, 1.9 mmol) at room temperature is added tetrabutylammonium fluoride (5.68 mL, 1 M THF, 5.68 mmol). After 2 h, the solution is evaporated and chromatographed on silica (95% CH2Cl2/5% CH3OH) to give 0.74 g (75.2%) of (R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-N-((3S,6R)-6-hydroxy-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl)-2-methoxy-acetamide as a white solid. 1H NMR 300 MHz δ 8.52(m, 2H), 7.69 (m, 1H), 7.29 (m, 1H), 5.77 (d, 1H), 5.54(dd, 1H), 4.69 (m, 2H), 4.29 (m, 2H), 4.10 (m, 2H), 3.92 (d, 1H), 3.54 (m, 2H), 3.50 (s, 3H), 3.33 (m,2H), 2.15 (m, 1H), 2.00 (m, 1H), 1.90 (m, 1H), 1.67 (m, 3H), 1.46 (m, 4H), 1.04 (s, 9H), 1.00 (t, 2H); MS (ESI) 520.2 (M+H)+.

Workup

  1. customthe solution is evaporated
  2. customchromatographed on silica (95% CH2Cl2/5% CH3OH)

Sources & evidence

ORD record
ord-91b7444b66d448cd8641516be0fac2d0
Source dataset
uspto-grants-2008_05
Patent number
US07378410B2

Reaction notes

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