Dichloromethane → HCID 25168565, compound

HRID 1175298Notes

Reaction equation

HRID 1175298 reaction equation
[CH2:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([Cl:12])[C:9]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([CH2:20][CH3:21])=[CH:16][CH:15]=2)=[CH:8][C:7]=1[C:22]1(OC)[C@H:27]([OH:28])[C@@H:26]([OH:29])[C@H:25]([OH:30])[C@@H:24]([CH2:31][OH:32])[O:23]1)[CH:2]=[CH2:3].C(Cl)Cl.C([SiH](CC)CC)C.B(F)(F)F.CCOCC>CC#N>[CH2:1]([O:4][CH2:5][C:6]1[CH:11]=[C:10]([Cl:12])[C:9]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([CH2:20][CH3:21])=[CH:16][CH:15]=2)=[CH:8][C:7]=1[C@H:22]1[C@H:27]([OH:28])[C@@H:26]([OH:29])[C@H:25]([OH:30])[C@@H:24]([CH2:31][OH:32])[O:23]1)[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8000Boron trifluoride etherateHCID 12052TriethylsilaneHCID 68743793HCID 68743793, compound

Product 1

HCID 25168565HCID 25168565, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a cooled solution (−15° C.) of (3R,4S,5S,6R)-2-(2-(allyloxymethyl)-4-chloro-5-(4-ethylbenzyl)phenyl)-6-(hydroxymethyl)-2-methoxytetrahydro-2H-pyran-3,4,5-triol in 1:1 CH2Cl2:CH3CN was added triethylsilane followed by addition of BF3.Et2O at a rate such that the temperature was maintained between −15° C. and −10° C. under argon. The reaction mixture was stirred for 4 h prior to being quenched by satd NaHCO3. It was evaporated and the residue was partitioned between EtOAc and water. The organic layer was separated, washed 2× with brine and dried over Na2SO4. Concentration gave a residue, which was purified by preparative TLC (EtOAc:MeOH=20:1, Rf=0.6) to yield 58 mg of title compound as a white solid. 1H-NMR (CD3OD, 400 MHz) δ 7.46 (s, 1H), 7.35 (s, 1H), 7.04 (s, 4H), 5.92-5.86 (m, 1H), 5.25 (dd, J=17.2 Hz, 1.6 Hz, 1H), 5.09 (dd, J=10.4 Hz, 1.6 Hz, 1H), 4.68 (m, 3H), 4.48 (d, J=9.2 Hz, 1H), 4.05-3.86 (m, 4H), 3.83 (dd, J=12.4 Hz, 2.4 Hz, 1H), 3.71-3.62 (m, 2H), 3.50-3.46 (m, 1H), 3.26-3.22 (m, 1H), 2.78-2.74 (m, 1H), 1.13 (d, J=7.2 Hz, 6H); LC-MS (m/z) 463 [(M+1)+].

Workup

  1. temperaturewas maintained between −15° C. and −10° C. under argon
  2. customto being quenched by satd NaHCO3
  3. customIt was evaporated
  4. customthe residue was partitioned between EtOAc and water
  5. customThe organic layer was separated
  6. washwashed 2× with brine
  7. dry with materialdried over Na2SO4
  8. concentrationConcentration
  9. customgave a residue, which
  10. customwas purified by preparative TLC (EtOAc:MeOH=20:1, Rf=0.6)

Sources & evidence

ORD record
ord-dd72d4a4ea814ee5a6e1d1e7f0402f4b
Source dataset
uspto-grants-2010_11
Patent number
US07838498B2

Reaction notes

Loading…