2,6-Lutidine → HCID 86717770, compound

HRID 513364Notes

Reaction equation

HRID 513364 reaction equation
[Si:1]([O:8]S(C(F)(F)F)(=O)=O)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].O[C@@H:17]1[N:23]([C:24]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][C:31]([NH:34][C:35](=[O:52])[C@@H:36]([NH:38][C:39](=[O:51])[C@@H:40]([NH:44][C:45]([O:47][CH2:48][CH:49]=[CH2:50])=[O:46])[CH:41]([CH3:43])[CH3:42])[CH3:37])=[CH:30][CH:29]=2)=[O:25])[C:22]2[CH:53]=[C:54]([O:59][Si:60]([CH:67]([CH3:69])[CH3:68])([CH:64]([CH3:66])[CH3:65])[CH:61]([CH3:63])[CH3:62])[C:55]([O:57][CH3:58])=[CH:56][C:21]=2[C:20](=[O:70])[N:19]2[CH:71]=[C:72](/[CH:74]=[CH:75]/[CH3:76])[CH2:73][C@@H:18]12.N1C(C)=CC=CC=1C>C(Cl)Cl>[Si:1]([O:8][C@@H:17]1[N:23]([C:24]([O:26][CH2:27][C:28]2[CH:29]=[CH:30][C:31]([NH:34][C:35](=[O:52])[C@@H:36]([NH:38][C:39](=[O:51])[C@@H:40]([NH:44][C:45]([O:47][CH2:48][CH:49]=[CH2:50])=[O:46])[CH:41]([CH3:42])[CH3:43])[CH3:37])=[CH:32][CH:33]=2)=[O:25])[C:22]2[CH:53]=[C:54]([O:59][Si:60]([CH:61]([CH3:63])[CH3:62])([CH:67]([CH3:69])[CH3:68])[CH:64]([CH3:65])[CH3:66])[C:55]([O:57][CH3:58])=[CH:56][C:21]=2[C:20](=[O:70])[N:19]2[CH:71]=[C:72](/[CH:74]=[CH:75]/[CH3:76])[CH2:73][C@@H:18]12)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 90116572HCID 90116572, compound

Product 1

HCID 86717770HCID 86717770, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Tert-butyldimethylsilyltrifluoromethane sulfonate (0.46 g, 1.74 mmol, 3.0 eq) was added to a solution of secondary alcohol 16 (0.5 g, 0.58 mmol, 1.0 eq) and 2,6-lutidine (0.25 g, 2.32 mmol, 4.0 eq) in dry DCM (10 mL) at 0° C. under an atmosphere of nitrogen. After 10 minutes, the reaction mixture was allowed to warm to room temperature and stirred for a further 120 mins. The organic phase was then washed successively with water (10 mL), saturated sodium bicarbonate (10 mL) and brine (5 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 50/50 v/v n-hexane/EtOAc) to afford the product as a white solid (0.320 g, 57%). LC/MS (4.415 min (ES+)), m/z: 976.52 [M+H]+. 1H NMR (400 MHz, CDCl3) δ 8.31 (br s, 1H), 7.48 (d, 2H, J=8.0 Hz), 7.21 (s, 1H), 7.14 (d, 2H, J=8.3 Hz), 6.89 (s, 1H), 6.65 (s, 1H), 6.38 (d, 1H, J=7.3 Hz), 6.25 (d, 1H, J=14.6 Hz), 5.93 (m, 1H), 5.85 (d, 1H, J=8.8 Hz), 5.50 (m, 1H), 5.34 (m, 1H), 5.24 (m, 2H), 5.15 (d, 1H, J=12.5 Hz), 4.86 (d, 1H, J=12.2 Hz), 4.62 (m, 3H), 4.01 (m, 1H), 3.86 (s, 3H), 3.78 (m, 1H), 3.04 (m, 1H), 2.56 (m, 1H), 2.20 (m, 1H), 1.84 (dd, 3H, J=6.6, 0.7 Hz), 1.48 (d, 3H, J=6.8 Hz), 1.20 (m, 3H), 1.05 (d, 9H, J=2.9 Hz), 1.03 (d, 9H, J=2.9 Hz), 0.99 (d, 3H, J=6.8 Hz), 0.95 (d, 3H, J=6.8 Hz), 0.88 (s, 9H), 0.27 (s, 3H), 0.14 (s, 3H).

Workup

  1. washThe organic phase was then washed successively with water (10 mL), saturated sodium bicarbonate (10 mL) and brine (5 mL)
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by flash chromatography (silica gel, 50/50 v/v n-hexane/EtOAc)

Sources & evidence

ORD record
ord-f702c120db0442fe8f37bc103521ea6e
Source dataset
uspto-grants-2015_08
Patent number
US09102704B2

Reaction notes

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