HCID 57814787, compound → HCID 57814803, compound

HRID 1254175Notes

Reaction equation

HRID 1254175 reaction equation
[Si:1]([O:8][C@H:9]([CH3:42])[CH2:10][CH2:11][CH2:12][C:13](=[O:41])/[CH:14]=[CH:15]/[C@H:16]1[C@H:20]([O:21][CH:22]2[CH2:27][CH2:26][CH2:25][CH2:24][O:23]2)[CH2:19][C@@H:18]([Cl:28])[C@@H:17]1[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][C:35]([O:37][CH2:38][CH2:39][CH3:40])=[O:36])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>ClCCl>[Si:1]([O:8][C@H:9]([CH3:42])[CH2:10][CH2:11][CH2:12][C@H:13]([OH:41])/[CH:14]=[CH:15]/[C@H:16]1[C@H:20]([O:21][CH:22]2[CH2:27][CH2:26][CH2:25][CH2:24][O:23]2)[CH2:19][C@@H:18]([Cl:28])[C@@H:17]1[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][C:35]([O:37][CH2:38][CH2:39][CH3:40])=[O:36])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

3

Reactant 1

HCID 57814787HCID 57814787, compound

Product 1

HCID 57814803HCID 57814803, compoundYield 74.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of enone 13 (425 mg, 0.67 mmol) in 7 mL of dichloromethane was cooled to −30° C. and stirred rapidly while solid (R)-methylCBS-borane complex (350 mg, 1.20 mmol) was added in one portion. The resulting solution was stirred at −30° to −20° C. for 1 h. TLC analysis at this stage showed no starting material left and the reaction mixture was quenched with 2 mL of methanol, the cooling bath was removed and the mixture was stirred at 25° C. 60 min. The mixture was concentrated in vacuo to remove solvents and the residual products were purified by FCC on silica gel (40 g Silicycle cartridge, 500 mL of 10% EA-hexanes, then 500 mL of 20% EA-hexanes) to yield 316 mg (74% yield) of (15S)-alcohol 14; 1H NMR (CDCl3): 0.04 (s, 6H), 0.87 (s, 9H), 0.93 (t, J=6 Hz, 3H), 1.10 (d, J=4.8 Hz, 3H), 1.24-1.88 (m, 24H), 2.10-2.32 (m, 4H), 3.45 (m, 1H), 3.80 (m, 2H), 4.03 (m, 4H), 4.61 (dt, J=2.4, 14.4 Hz, 1H), 5.56 (m, 2H).

Workup

  1. additionwas added in one portion
  2. stirringThe resulting solution was stirred at −30° to −20° C. for 1 h
  3. waitleft
  4. customthe reaction mixture was quenched with 2 mL of methanol
  5. customthe cooling bath was removed
  6. stirringthe mixture was stirred at 25° C
  7. custom60 min
  8. concentrationThe mixture was concentrated in vacuo
  9. customto remove solvents
  10. customthe residual products were purified by FCC on silica gel (40 g Silicycle cartridge, 500 mL of 10% EA-hexanes

Sources & evidence

ORD record
ord-57d6a2051f904e9da43db3124ca270d2
Source dataset
uspto-grants-2013_06
Patent number
US08455547B2

Reaction notes

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