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 1354485Notes

Reaction equation

HRID 1354485 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) δ 1.37 (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-194a9b6d47d44600a9be15d517627a82
Source dataset
uspto-grants-2007_05
Patent number
US07223798B2

Reaction notes

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