Acetic Acid → 2-[[(4S,5R)-5-[(1E,3E)-1,3-hexadien-5-ynyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methoxy]ethanoic acid, methyl ester

HRID 1671730Notes

Reaction equation

HRID 1671730 reaction equation
[CH:1](/[C@H:7]1[O:11][C:10]([CH3:13])([CH3:12])[O:9][C@H:8]1[CH2:14][O:15][CH2:16][C:17]([OH:19])=[O:18])=[CH:2]\[CH:3]=[CH:4]\[C:5]#[CH:6].[CH3:20][Si](C=[N+]=[N-])(C)C.[N+](=C)=[N-].C(O)(=O)C>C1COCC1.CCOCC>[CH:1](/[C@H:7]1[O:11][C:10]([CH3:13])([CH3:12])[O:9][C@H:8]1[CH2:14][O:15][CH2:16][C:17]([O:19][CH3:20])=[O:18])=[CH:2]\[CH:3]=[CH:4]\[C:5]#[CH:6]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 9550DiazomethaneHCID 167693TrimethylsilyldiazomethaneHCID 865887712-[[(4S,5R)-5-[(1E,3E)-1,3-hexadien-5-ynyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methoxy]ethanoic acid

Product 1

HCID 865887732-[[(4S,5R)-5-[(1E,3E)-1,3-hexadien-5-ynyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methoxy]ethanoic acid, methyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 2-[[(4S,5R)-5-[(1E,3E)-1,3-hexadien-5-ynyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methoxy]ethanoic acid in THF was cooled in an ice bath and treated with a solution of trimethylsilyldiazomethane in THF in portions. Excess diazomethane was decomposed with acetic acid and the mixture was diluted with ether and washed with water, saturated sodium bicarbonate, water (2×), and brine, dried, treated with silica gel and concentrated. Purification by chromatography on silica gel using a gradient of ether in hexane gave 0.9 g of 2-[[(4S,5R)-5-[(1E,3E)-1,3-hexadien-5-ynyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methoxy]ethanoic acid, methyl ester, a compound of formula (W), as an oil: 1H NMR (CDCl3) δ1.37 (s, 3H), 1.51 (s, 3H), 3.06 (s, 1H), 3.49 (m, 2H), 3.74 (s, 3H), 4.16 (m, 2H), 4.42 (m, 1H), 4.65 (t, 1H), 5.60 (dd, 1H), 5.79 (dd, 1H), 6.33 (dd, 1H), 6.65 (dd, 1H) ppm.

Workup

  1. washwashed with water, saturated sodium bicarbonate, water (2×), and brine
  2. customdried
  3. additiontreated with silica gel
  4. concentrationconcentrated
  5. customPurification by chromatography on silica gel using a gradient of ether in hexane

Sources & evidence

ORD record
ord-96e51170a63e4912b1204cb8f9599239
Source dataset
uspto-grants-2011_08
Patent number
US07994346B2

Reaction notes

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