Tetrahydrofuran → (1R,4S)-4-{(2R)-2-[(1R,7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-1-methyl-2-cyclopenten-1-ol

HRID 567406Notes

Reaction equation

HRID 567406 reaction equation
[CH3:1][Si:2]([CH3:24])([CH3:23])[O:3][CH:4]1[CH2:12][CH2:11][CH2:10][C@@:9]2([CH3:13])[CH:5]1[CH2:6][CH2:7][C@@H:8]2[C@H:14]([CH3:22])[CH2:15][C@H:16]1[CH2:20][C:19](=[O:21])[CH:18]=[CH:17]1.O1CCC[CH2:26]1.C[Li]>CCOCC>[CH3:24][Si:2]([CH3:23])([CH3:1])[O:3][CH:4]1[CH2:12][CH2:11][CH2:10][C@@:9]2([CH3:13])[CH:5]1[CH2:6][CH2:7][C@@H:8]2[C@H:14]([CH3:22])[CH2:15][C@H:16]1[CH2:20][C@@:19]([CH3:26])([OH:21])[CH:18]=[CH:17]1

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 57055066(4S)-4-{(2R)-2-[(1R, 7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-2-cyclopenten-1-oneHCID 178418348HCID 178418348, compound2×

Product 1

HCID 57292270(1R,4S)-4-{(2R)-2-[(1R,7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-1-methyl-2-cyclopenten-1-olYield 84%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-78 °C

Procedure

A 1.76 g amount of the compound (1-10), (4S)-4-{(2R)-2-[(1R, 7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-2-cyclopenten-1-one was placed into a 300 ml eggplant-shaped flask. A 150 ml amount of tetrahydrofuran was added and the solution stirred and cooled to −78° C., and then, 6.5 ml of an ether solution of methyllithium (1.16 mol/liter) was added, followed by stirring for 15 minutes. A 50 ml amount of saturated saline was added, the excess methyllithium was broken down, then 100 ml of ether was added for separation. The organic layer was washed with saturated saline, then was dried over anhydrous magnesium sulfate. The desiccant was filtered out, the solvent was distilled off under reduced pressure, and the crude product was purified by a silica gel column (Merck gel: 300 g, hexane/ethyl acetate=15/1 to 9/1) to obtain the desired product (1-11), (1R,4S)-4-{(2R)-2-[(1R,7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-1-methyl-2-cyclopenten-1-ol in an amount of 1.55 g (yield 84%) and the desired product (1-12), (1S,4S)-4-{(2R)-2-[(1R,7aR)-octahydro-4-trimethylsilyloxy-7a-methyl-1H-inden-1-yl]-propyl}-1-methyl-2-cyclopenten-1-ol, in an amount of 0.27 g (yield 14%).

Workup

  1. stirringby stirring for 15 minutes
  2. additionA 50 ml amount of saturated saline was added
  3. washThe organic layer was washed with saturated saline
  4. dry with materialwas dried over anhydrous magnesium sulfate
  5. filtrationThe desiccant was filtered out
  6. distillationthe solvent was distilled off under reduced pressure
  7. customthe crude product was purified by a silica gel column (Merck gel: 300 g, hexane/ethyl acetate=15/1 to 9/1)

Sources & evidence

ORD record
ord-8b0e970f44fe4152be7336a682de1f93
Source dataset
uspto-grants-2001_01
Patent number
US06177586B1

Reaction notes

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