Methyl iodide → HCID 57672450, compound

HRID 2101807Notes

Reaction equation

HRID 2101807 reaction equation
[CH:1]([N-]C(C)C)(C)C.[Li+].[C:9]1([CH2:15][O:16][C:17]2[CH:22]=[CH:21][C:20]([C@H:23](/[CH:29]=[CH:30]\[CH3:31])[CH2:24][C:25]([O:27][CH3:28])=[O:26])=[CH:19][CH:18]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.IC>C1COCC1>[CH3:1][C@@H:24]([C@H:23]([C:20]1[CH:19]=[CH:18][C:17]([O:16][CH2:15][C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)=[CH:22][CH:21]=1)/[CH:29]=[CH:30]\[CH3:31])[C:25]([O:27][CH3:28])=[O:26]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 2724682Lithium diisopropylamideHCID 57672476HCID 57672476, compound

Product 1

HCID 57672450HCID 57672450, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of lithium diisopropylamide (0.2 mL, 2 mmol in heptane/THF/ethylbenzene) in THF (1.0 mL) was slowly added (S,Z)-methyl 3-(4-(benzyloxy)phenyl)hex-4-enoate 41.1 (0.50 g, 2 mmol) in THF (5.0 mL) at −78° C. The resulting mixture was stirred at −78° C. for 1 hour and then iodomethane (0.1 mL, 2 mmol) was added. The reaction mixture was stirred at the same temperature for 20 minutes, and then stirred at room temperature for 16 hours. The solvent was removed in vacuo. The residue was purified by silica gel, eluent with hexane/EtOAc 95/5 to 10/90 to give the title compound as a major product 41.2 in a ratio of 95:5. 1H NMR (400 MHz, CDCl3) δ ppm 1.08 (d, J=7.04 Hz, 3H) 1.46-1.61 (m, 1H) 2.64 (m, 1H) 3.34 (s, 3H) 4.90 (s, 2H) 5.35-5.53 (m, 2H) 6.76-6.84 (m, 2H) 6.97-7.07 (m, 2H) 7.15-7.34 (m, 5H). MS ESI (pos.) m/e: 325.1 (M+H)+. It is possible that the stereochemistry at the carbon atom adjacent to the carbonyl is opposite that shown which would carry through to the final product of this Example. However, it is believed that the structure of 41.2 is as shown above.

Workup

  1. customat −78° C
  2. stirringThe reaction mixture was stirred at the same temperature for 20 minutes
  3. stirringstirred at room temperature for 16 hours
  4. customThe solvent was removed in vacuo
  5. customThe residue was purified by silica gel, eluent with hexane/EtOAc 95/5 to 10/90

Sources & evidence

ORD record
ord-51f3adc42a074ff1a8788f95d637c09e
Source dataset
uspto-grants-2009_08
Patent number
US07572934B2

Reaction notes

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