tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-9-methyl-8-(2-methylallyloxy)-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamate → tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-8-isobutoxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamate

HRID 75738Notes

Reaction equation

HRID 75738 reaction equation
[CH2:1]([C@@H:8]1[C@@H:16]([O:17][CH2:18][C:19]([CH3:21])=[CH2:20])[C@H:15]([CH3:22])[O:14][C:13](=[O:23])[C@@H:12]([N:24]([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[C:25](=[O:31])[O:26][C:27]([CH3:30])([CH3:29])[CH3:28])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H][H]>CCOC(C)=O.[Pd]>[CH2:1]([C@@H:8]1[C@@H:16]([O:17][CH2:18][CH:19]([CH3:21])[CH3:20])[C@H:15]([CH3:22])[O:14][C:13](=[O:23])[C@@H:12]([N:24]([C:25]([O:26][C:27]([CH3:28])([CH3:29])[CH3:30])=[O:31])[C:32](=[O:33])[O:34][C:35]([CH3:36])([CH3:37])[CH3:38])[CH2:11][O:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 86701229tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-9-methyl-8-(2-methylallyloxy)-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamateHCID 178418361HCID 178418361, compound

Product 1

HCID 86701230tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-8-isobutoxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamateYield 99%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-9-methyl-8-(2-methylallyloxy)-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamate (3.65 g, 6.84 mmol, 1.00 equiv) in EtOAc (68 ml) was added Pd/C (10%; 0.364 g, 0.342 mmol, 0.0500 equiv). The atmosphere was replaced with hydrogen (1 atm, balloon) and the mixture was stirred vigorously overnight. The reaction was filtered through a plug of Celite® and the plug was then flushed with EtOAc (100 mL). The filtrate was concentrated to give tert-butyl N-[(3S,7S,8R,9S)-7-benzyl-8-isobutoxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamate (3.62 g, 99%) as a white, crystalline solid: IR (ATR) 2987, 2933, 2914, 2876, 1749, 1723, 1413, 1391, 1367, 1317, 1271, 1257, 1238, 1229, 1196, 1147, 1097, 1084, 1065, 1058, 854, 744 cm−1; 1H NMR (400 MHz, CDCl3) δ 3.33-3.27 (m, 1H), 3.40-3.33 (m, 1H), 1.92-1.79 (m, 1H), 7.35-7.22 (m, 2H), 7.22-7.11 (m, 3H), 5.11 (dd, J=8.5, 6.4 Hz, 1H), 4.88 (dq, J=9.0, 6.3 Hz, 1H), 3.46-3.40 (m, 1H), 4.07 (dd, J=11.8, 6.4 Hz, 1H), 3.84 (dd, J=11.8, 8.6 Hz, 1H), 3.52 (d, J=10.6 Hz, 1H), 3.18-3.08 (m, 2H), 2.35 (s, 1H), 1.98 (s, 1H), 1.48 (s, 21H), 0.94 (d, J=6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 169.98, 152.62, 140.12, 129.25, 128.32, 125.99, 84.52, 82.99, 78.82, 75.39, 70.96, 57.47, 47.05, 34.98, 29.16, 27.92, 19.49, 18.95; HRMS-ESI (m/z) [M−H]− calc'd for C29H44NO8; 534.3072. found, 534.3069.

Workup

  1. filtrationThe reaction was filtered through a plug of Celite®
  2. customthe plug was then flushed with EtOAc (100 mL)
  3. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-f5131b8b3b6b41d383c31e5f15329748
Source dataset
uspto-grants-2014_09
Patent number
US08835462B2

Reaction notes

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