Triphenylphosphine Oxide → HCID 12003215, compound

HRID 599525Notes

Reaction equation

HRID 599525 reaction equation
[CH3:1][C:2]12[CH2:9][O:8][C:5]([CH2:10][CH2:11][CH2:12]/[CH:13]=[CH:14]\[CH2:15][C@@H:16]3[C@@H:20]([CH2:21][S:22]([C:25]4[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=4)(=[O:24])=[O:23])[C@H:19]([O:31][Si](CC)(CC)CC)[CH2:18][C@@H:17]3[OH:39])([O:6][CH2:7]1)[O:4][CH2:3]2.C1(P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>>[CH3:1][C:2]12[CH2:7][O:6][C:5]([CH2:10][CH2:11][CH2:12]/[CH:13]=[CH:14]\[CH2:15][C@@H:16]3[C@@H:20]([CH2:21][S:22]([C:25]4[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=4)(=[O:24])=[O:23])[C@H:19]([OH:31])[CH2:18][C@@H:17]3[OH:39])([O:4][CH2:3]1)[O:8][CH2:9]2

Participants

3

Reactant 2

HCID 13097Triphenylphosphine OxideHCID 12003297HCID 12003297, compound

Product 1

HCID 12003215HCID 12003215, compound

Procedure

The mixture of (1R,2R,3R,4S)-3-[(Z)-6-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)hexe-2-nyl]-2-[(phenylsulfonyl)methyl]-4-(triethylsilyloxy)cyclopentanol (ca. 65%) and (1S,2R,3R,4R)-2-[(Z)-6-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)hex-2-enyl]-3-[(phenylsulfonyl)methyl]-4-(triethylsilyloxy)cyclopentanol (ca. 35%) (584 mg of the mixture, yield 15.4%), colorless glaze was obtained; 1H-NMR (CDCl3; 200 MHz) δ 0.57 (6H, 2×q), 0.79 (1.95H, s), 0.80 (1.05H, s), 0.93 (9H, 2×t), 1.34-1.54 (3.5H, m), 1.56-1.78 (3H, m), 1.82-2.20 (6.6H, m), 3.01 (0.65H, dd: 14.4, 11.2 Hz), 3.32 (0.65H, dd: 14.4, 2.6 Hz), 3.56 (0.65H, m), 3.88 (3.9H, s), 3.89 (2.1H, s), 3.90 (0.35H, m), 4.13 (1.30H, m), 5.15-5.38 (2H, m), 7.54-7.74 (3H, m), 7.93-7.99 (2H, m); fractions prepared after washing out with Phase II were combined on the basis of TLC chromatograms, concentrated and dried under vacuum. Glaze was obtained (3.597 g) containing slight amount of triphenylphosphine oxide, which was removed by two-time maceration with Et2O (8 mL, 4 mL). (1R,3S,4R,5R)-4-[(Z)-6-(4-Methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)hex-2-enyl]-5-[(phenylsulfonyl)methyl]cyclopentane-1,3-diol was prepared (2.0 g, 65.5%); 1H-NMR (CDCl3; 200 MHz) δ 0.80 (3H, s), 1.36-1.52 (3H, m), 1.61 (2H, m), 1.8-2.29 (8H, m), 3.05 (1H, dd: 14.3, 11.2 Hz), 3.33 (1H, dd: 14.3, 2.6 Hz), 3.53 (1H, bs, OH), 3.88 (6H, s), 4.09 (1H, m), 4.31 (1H, m), 5.17-5.39 (2H, m), 7.47-7.74 (3H, m), 7.93-7.99 (2H, m).

Workup

  1. customcolorless glaze was obtained
  2. customfractions prepared
  3. washafter washing out with Phase II
  4. concentrationconcentrated
  5. customdried under vacuum
  6. customGlaze was obtained (3.597 g)
  7. customwas removed by two-time maceration with Et2O (8 mL, 4 mL)

Sources & evidence

ORD record
ord-cb6c530fc59644b88b555b9c35d9d625
Source dataset
uspto-grants-2011_03
Patent number
US07897793B2

Reaction notes

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