HCID 67285850, compound → HCID 68772872, compound

HRID 2191371Notes

Reaction equation

HRID 2191371 reaction equation
C(=O)(OC)O[C@@H:3]1[C@H:10]2[C@H:6]([O:7][C:8]([CH3:12])([CH3:11])[O:9]2)[C:5]([CH2:13][O:14][C:15]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:4]1.[Cu]C#N.[CH:40]([Mg]Br)=[CH2:41]>C1COCC1>[CH3:11][C:8]1([CH3:12])[O:7][C@@H:6]2[C:5]([CH2:13][O:14][C:15]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)=[CH:4][C@@H:3]([CH:40]=[CH2:41])[C@@H:10]2[O:9]1

Participants

5

Reactant 3

HCID 67285850HCID 67285850, compoundHCID 178418507HCID 178418507, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 68772872HCID 68772872, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

(3aS,4S,6aR)-2,2-dimethyl-6-(trityloxymethyl)-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-yl methyl carbonate (1-2) (1.2 g, 2.19 mmol, 1 equiv) was dissolved in anhydrous THF (22 mL) and cooled to 0° C. To the resulting mixture was added copper(I) cyanide (65 mg, 0.72 mmol, 0.33 equiv) followed by 0.7 M vinylmagnesium bromide solution in THF (7.84 mL, 5.49 mmol, 2.5 equiv). After 1 h at 0° C., the reaction was quenched with NH4Cl (10 mL) and extracted with Et2O (3×25 mL). The combined organic extracts were washed with water, dried (MgSO4), and concentrated. Purification via flash chromatography on silica gel column (ethyl acetate/hexanes) gave (3aS,4R,6aR)-2,2-dimethyl-6-(trityloxymethyl)-4-vinyl-4,6a-dihydro-3aH-cyclopenta[d][1,3]dioxole (1-3). 1H NMR (500 MHz, CDCl3) δ 7.25-7.55 (m, 15H), 5.94 (brd, 1H, J=0.5 Hz), 5.85 (ddd, 1H, J=7.5, 3, 17.5 Hz), 5.18 (dt, 1H, J=1.5, 17.5 Hz), 5.12 (dd, 1H, J=1, 10 Hz), 5.07 (d, 1H, J=5.5 Hz), 4.52 (d, 1H, J=6 Hz), 3.93 (d, 1H, J=14 Hz), 3.76 (d, 1H, J=14 Hz), 3.53 (d, 1H, J=7.5 Hz), 1.43 (s, 3H), 1.37 (s, 3H).

Workup

  1. customthe reaction was quenched with NH4Cl (10 mL)
  2. extractionextracted with Et2O (3×25 mL)
  3. washThe combined organic extracts were washed with water
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customPurification via flash chromatography on silica gel column (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-58041dc532c74c93938c0c4eb2d1e41c
Source dataset
uspto-grants-2012_12
Patent number
US08329697B2

Reaction notes

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