Methanol → HCID 42636427, compound

HRID 1092441Notes

Reaction equation

HRID 1092441 reaction equation
C([O:8][CH2:9][C@H:10]1[C:15](=[CH2:16])[C@@H:14]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([CH2:31][CH3:32])=[CH:27][CH:26]=3)[CH:18]=2)[C@H:13]([O:33]CC2C=CC=CC=2)[C@@H:12]([O:41]CC2C=CC=CC=2)[C@@H:11]1[O:49]CC1C=CC=CC=1)C1C=CC=CC=1.B(Cl)(Cl)Cl.CO>C(Cl)Cl>[Cl:23][C:20]1[CH:21]=[CH:22][C:17]([C@@H:14]2[C:15](=[CH2:16])[C@H:10]([CH2:9][OH:8])[C@@H:11]([OH:49])[C@H:12]([OH:41])[C@H:13]2[OH:33])=[CH:18][C:19]=1[CH2:24][C:25]1[CH:26]=[CH:27][C:28]([CH2:31][CH3:32])=[CH:29][CH:30]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 25135Boron TrichlorideHCID 66588515HCID 66588515, compound

Product 1

HCID 42636427HCID 42636427, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of ((1S,2R,3R,4R,6S)-4-(benzyloxymethyl)-6-(4-chloro-3-(4-ethylbenzyl)phenyl)-5-methylenecyclohexane-1,2,3-triyl)tris(oxy)tris(methylene)tribenzene (34, 24 mg, 31.4 mmol) in anhydrous DCM (0.8 mL) in a vial at −78° C. under a nitrogen blanket was added BCl3 (1 M in DCM, 0.25 mL) drop-wise over 15 minutes. The resulting mixture was stirred at −78° C. for 30 minutes and gradually warmed to −20° C. The resulting mixture was stirred at −20° C. for another 30 minutes. At this time, LC-MS indicated that the reaction was complete. The solution was cooled to −78° C. and methanol (1 mL) was slowly added. The resulting solution was warmed to room temperature and concentrated under reduced pressure. The residue was dissolved in 0.5 mL of 1:1 DCM:MeOH and loaded on a preparative TLC plate, which was developed in 15:1 (DCM:MeOH) to obtain 9 mg (71%) of compound 35 as a white solid. 1H NMR (300 MHz, CDCl3) δ 7.29-6.89 (m, 7H), 4.80 (s, 1H), 4.28 (s, 1H), 3.95 (m, 4H), 3.64 (m, 2H), 3.51(m, 3H), 3.22 (m, 1H), 2.58 (q, J=7.2 Hz, 2H), 2.25 (m, 1H), 1.18 (t, J=7.5 Hz, 3H). LC-ESI-MS m/z 425 (M+Na).

Workup

  1. temperaturegradually warmed to −20° C
  2. stirringThe resulting mixture was stirred at −20° C. for another 30 minutes
  3. temperatureThe solution was cooled to −78° C.
  4. temperatureThe resulting solution was warmed to room temperature
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in 0.5 mL of 1:1 DCM

Sources & evidence

ORD record
ord-8dfc25b9d46f488bbb55a3057e296995
Source dataset
uspto-grants-2012_03
Patent number
US08129434B2

Reaction notes

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