2,6-Lutidine → HCID 11858568, compound

HRID 522183Notes

Reaction equation

HRID 522183 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@H:11]([CH2:32][I:33])[C@@H:10]1[OH:34])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C(C)=CC=CC=1C.[Si:43](OS(C(F)(F)F)(=O)=O)([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44]>C(Cl)Cl>[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@H:11]([CH2:32][I:33])[C@@H:10]1[O:34][Si:43]([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 10897111HCID 10897111, compound

Product 1

HCID 11858568HCID 11858568, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of (2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(iodomethyl)tetrahydro-2H-pyran-3-ol (1.0 g, 1.74 mmol, 1.0 equiv) in dry DCM (10 mL) under nitrogen atmosphere, was added 2,6-lutidine (0.41 mL, 3.5 mmol, 2.0 equiv) at room temperature. The resulting mixture was stirred for 5 minutes. The reaction was cooled to 0° C. and TBSOTf (0.6 mL, 2.6 mmol, 1.5 equiv) was added dropwise. The mixture was then slowly allowed to warm to room temperature. After 1 hour, the mixture was diluted with DCM (20 mL) and washed with water (2×20 mL). The organic layer was dried over Na2SO4 and over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give an oil. The oil was then purified by silica gel chromatography, eluting with 5% EtOAc in petroleum ether to give (((2S,3R,4S,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(iodomethyl)tetrahydro-2H-pyran-3-yl)oxy)(tert-butyl)dimethylsilane as a colorless oil (1.05 g, 94%). 1H NMR (400 MHz, CDCl3) δ 7.40-7.22 (m, 13H), 7.09-7.04 (m, 2H), 4.90-4.77 (m, 2H), 4.77-4.68 (m, 2H), 4.53 (d, J=12.1 Hz, 1H), 4.47 (d, J=10.7 Hz, 1H), 4.09 (ddd, J=12.2, 5.9, 3.4 Hz, 1H), 3.91 (dd, J=9.2, 5.9 Hz, 1H), 3.81 (dd, J=10.7, 3.2 Hz, 1H), 3.75 (dd, J=10.7, 2.1 Hz, 1H), 3.69 (dd, J=9.9, 8.7 Hz, 1H), 3.63-3.56 (m, 2H), 3.51 (dt, J=9.9, 2.6 Hz, 1H), 3.41 (t, J=11.8 Hz, 1H), 0.91 (s, 9H), 0.09 (s, 3H), 0.07 (s, 3H).

Workup

  1. temperatureto warm to room temperature
  2. waitAfter 1 hour
  3. washwashed with water (2×20 mL)
  4. dry with materialThe organic layer was dried over Na2SO4 and over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give an oil
  8. customThe oil was then purified by silica gel chromatography
  9. washeluting with 5% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-b3857e16dc1d4fd38dcd7fe797a55a6b
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

Loading…