Tetrahydrofuran → (+)-1-(4-Methoxyphenyl)-1-phenoxy-2-propene

HRID 14432Notes

Reaction equation

C([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[O:10][CH2:11][CH:12]=[CH2:13])(C)C.[O-:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Li+].[CH2:22]1COCC1>>[CH3:22][O:14][C:15]1[CH:20]=[CH:19][C:18]([CH:11]([O:10][C:5]2[CH:4]=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH:12]=[CH2:13])=[CH:17][CH:16]=1

Participants

Reactant 3

HCID 8028Tetrahydrofuran

HCID 637355Allyl o-i-propylphenyl ether

HCID 11815295Lithium phenoxide

Product 1

HCID 9881246(+)-1-(4-Methoxyphenyl)-1-phenoxy-2-propene

Procedure

(−)-i-Propyl allyloxybenzene (Evans, P. A.; Leahy, D. K. J. Am. Chem. Soc. 2000, 122, 5012): The general procedure was followed with lithium phenoxide (200 mg, 2.0 mmol) and 2-hexenyl methylcarbonate (160 mg, 1.0 mmol) in THF (2 mL). The reaction was conducted at 50° C. for 14 h. 1H NMR analysis of the mixture indicated the ratio of regioisomers to be 92/8. The residue was purified by flash chromatography on silica gel (0-1% Et2O/Hexanes) to afford 162 mg of the title compound as an oil. [93%, Rf 0.90 (5% Et2O/Hexanes)]. 1H NMR (500 MHz, CDCl3) δ 7.23 (m, 2H), 6.91 (m, 3H), 5.84 (ddd, J=17.3, 10.6, 6.2 Hz, 1H), 5.25 (d, J=17.4 Hz, 1H), 5.20 (d, J=10.6 Hz, 1H), 4.59 (dt, J=6.8, 6.0 Hz, 1H), 1.83-1.74 (m, 1H), 1.68-1.61 (m, 1H), 1.58-1.38 (m, 2H), 0.96 (t, J=7.4 Hz, 3H); 13C NMR (125.77 MHz, CDCl3) δ 158.4, 138.2, 129.3, 120.6, 116.2, 116.0, 78.6, 37.7, 18.6, 14.0. HPLC analysis indicated an enantiomeric excess of 92% [Chiralcel® OD-H column, eluting with 99.9:0.1 hexane/i-PrOH, 0.6 mL/min, 220 nm; major enantiomer tR, 13.3, minor enantiomer tR 15.8 min].

Workup

customThe residue was purified by flash chromatography on silica gel (0-1% Et2O/Hexanes)

Sources & evidence

ORD record: ord-58b058c6b9d74253a7e942eae1eeed42
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07732365B2

Reaction notes

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