Diisopropylethylamine → tert-Butyl N-[(3R,4R,5S)-4-[(tert-butyldimethylsilyl)oxy]-5-methylpiperidin-3-yl]carbamate

HRID 924428Notes

Reaction equation

HRID 924428 reaction equation
CS(O[CH2:6][C@@H:7]([NH:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:8]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[C@@H:9]([CH3:14])[CH2:10][N:11]=[N+]=[N-])(=O)=O.CCN(C(C)C)C(C)C>CO.[Pd]>[Si:16]([O:15][C@@H:8]1[C@@H:9]([CH3:14])[CH2:10][NH:11][CH2:6][C@H:7]1[NH:23][C:24](=[O:25])[O:26][C:27]([CH3:30])([CH3:28])[CH3:29])([C:19]([CH3:21])([CH3:22])[CH3:20])([CH3:17])[CH3:18]

Participants

5

Reactant 2

HCID 81531DiisopropylethylamineHCID 59226467(2R,3R,4S)-5-azido-2-(tert-butoxycarbonylamino)-3-(tert-butyldimethylsilyloxy)-4-methylpentyl methanesulfonate

Product 1

HCID 70901078tert-Butyl N-[(3R,4R,5S)-4-[(tert-butyldimethylsilyl)oxy]-5-methylpiperidin-3-yl]carbamateYield 98%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of (2R,3R,4S)-5-azido-2-[(tert-butoxycarbonyl)amino]-3-{[tert-butyl(dimethyl)silyl]oxy}-4-methylpentyl methanesulfonate (0.59 g, 1.3 mmol) in MeOH (10 mL) was deoxygenated with nitrogen for 20 min. DIPEA (0.55 mL, 3.2 mmol) was added, followed by 10 wt % Pd on carbon (0.1 g, 0.1 mmol). The mixture was hydrogenated under hydrogen gas at 1 atm. for 2 h. The reaction mixture was then filtered and the filtrate was concentrated under reduced pressure to give the sub-title compound (0.43 g, 98%). LCMS calc. for C17H37N2O3Si (M+H)+: m/z=345.3. found: 345.2. 1H NMR (500 MHz, CDCl3) δ 4.35 (bs, 1H), 3.32 (dt, J=13.1, 6.3 Hz, 1H), 3.25 (d, J=12.3 Hz, 1H), 3.04 (t, J=8.8 Hz, 1H), 2.94 (ddd, J=13.1, 4.1, 1.5 Hz, 1H), 2.33 (dd, J=12.6, 10.5 Hz, 1H), 2.24 (dd, J=13.1, 10.9 Hz, 1H), 1.76 (bs, 1H), 1.55 (tdd, J=8.9, 6.7, 4.2 Hz, 1H), 1.41 (s, 9H), 0.92 (d, J=6.6 Hz, 3H), 0.87 (s, 9H), 0.07 (d, J=10.3 Hz, 6H) ppm.

Workup

  1. filtrationThe reaction mixture was then filtered
  2. concentrationthe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-b800598aec924fffa8ff5ffe09cd6f88
Source dataset
uspto-grants-2016_03
Patent number
US09278950B2

Reaction notes

Loading…