Triphenylphosphine → (S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoate

HRID 921119

Reaction equation

HRID 921119 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:9]([CH3:12])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH3:13][C@@H:14](O)[CH2:15][CH:16]=[CH2:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOCC>[CH3:12][C:9]1[CH:10]=[CH:11][C:2]([O:1][C@H:16]([CH2:15][CH:14]=[CH2:13])[CH3:17])=[C:3]([CH:8]=1)[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 89802Methyl 5-methylsalicylateHCID 5363146Diisopropyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-ol

Product 1

HCID 118307101(S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoateYield 90%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 2-hydroxy-5-methylbenzoate (1.0 g, 6.02 mmol) in THF (14 ml) were added (R)-(−)-pent-4-en-2-ol (1.037 g, 12.04 mmol) and triphenylphosphine (2.052 g, 7.82 mmol). DIAD (1.521 ml, 7.82 mmol) was added dropwise (exotherm) and the mixture was stirred at rt. After 4.5 h, the mixture was diluted with Et2O and washed with 1N NaOH followed by water (3×'s) then brine, dried (Na2SO4), filtered and concentrated. The yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV) to give (S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoate (1.2664 g, 5.41 mmol, 90% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J=2.2 Hz, 1H), 7.23 (dd, J=8.3, 2.0 Hz, 1H), 6.90 (d, J=8.6 Hz, 1H), 6.03-5.77 (m, 1H), 5.21-4.99 (m, 2H), 4.61-4.35 (m, 1H), 3.89 (s, 3H), 2.60-2.46 (m, 1H), 2.46-2.34 (m, 1H), 2.34-2.25 (m, 3H), 1.34 (d, J=6.1 Hz, 3H).

Workup

  1. washwashed with 1N NaOH
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV)

Sources & evidence

ORD record
ord-0623d862063447738561a0cabef1b5ef
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Linked notes

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