DOI: 10.1021/ol0001721. Epoxidation of <i>p</i>-Methoxycinnamates Using Chiral Dioxiranes Derived from New Trisubstituted Halogenated Cyclohexanones: Enhanced Efficiency of Ketones Having an Axial Halogen

Epoxidation of p-Methoxycinnamates Using Chiral Dioxiranes Derived from New Trisubstituted Halogenated Cyclohexanones: Enhanced Efficiency of Ketones Having an Axial Halogen

10.1021/ol0001721

Crossref journal-article

American Chemical Society (ACS)

Organic Letters (316)

Bibliography

SolladiÃ©-Cavallo, A., & BouÃ©rat, L. (2000). Epoxidation of p-Methoxycinnamates Using Chiral Dioxiranes Derived from New Trisubstituted Halogenated Cyclohexanones: Enhanced Efficiency of Ketones Having an Axial Halogen. Organic Letters, 2(23), 3531â3534.

Authors 2

A. Solladié-Cavallo (first)
L. Bouérat (additional)

References 14 Referenced 72

{'key': 'ol0001721b00001/ol0001721b00001_1', 'first-page': '492', 'volume': '118', 'author': 'Yang D.', 'year': '1996', 'journal-title': 'J. Am. Chem. Soc.'} / J. Am. Chem. Soc. by Yang D. (1996)
{'key': 'ol0001721b00001/ol0001721b00001_2', 'first-page': '2329', 'volume': '62', 'author': 'Wang Z. X.', 'year': '1997', 'journal-title': 'J. Org. Chem.'} / J. Org. Chem. by Wang Z. X. (1997)
{'key': 'ol0001721b00001/ol0001721b00001_3', 'first-page': '9807', 'volume': '118', 'author': 'Tu Y.', 'year': '1996', 'journal-title': 'J Am. Chem. So'} / J Am. Chem. So by Tu Y. (1996)
{'key': 'ol0001721b00002/ol0001721b00002_1', 'first-page': '8289', 'volume': '62', 'author': 'Denmark S. E.', 'year': '1997', 'journal-title': 'J. Org. Chem.'} / J. Org. Chem. by Denmark S. E. (1997)
{'key': 'ol0001721b00002/ol0001721b00002_2', 'first-page': '622', 'volume': '621', 'author': 'Armstrong A.', 'year': '1998', 'journal-title': 'Chem. Commun.'} / Chem. Commun. by Armstrong A. (1998)
{'key': 'ol0001721b00003/ol0001721b00003_1', 'first-page': '6458', 'volume': '64', 'author': 'Wang Z. X.', 'year': '1999', 'journal-title': 'J. Org. Chem.'} / J. Org. Chem. by Wang Z. X. (1999)
{'key': 'ol0001721b00004/ol0001721b00004_1', 'first-page': '941', 'volume': '11', 'author': 'Solladié-Cavallo A.', 'year': '2000', 'journal-title': 'Tetrahedron: Asymmetry'} / Tetrahedron: Asymmetry by Solladié-Cavallo A. (2000)
(a)Procedure A.Distilled water (6 mL) and a solution (4 mL) of acetic acid (0.5 mL) and 0.1 M aqueous K2CO3(100 mL) are added under stirring to a solution of 1 mmol of methylp-methoxycinnamate6a(0.192 g, 1 equiv) and 0.1 or 0.3 mmol of ketone (0.1 or 0.3 equiv) in dioxane (16 mL). The mixture is cooled to the desired temperature, and a solution of oxone (1.850 g, 3 mmol, 6 equiv of oxidant) in distilled water (7 mL) is added dropwise over 6 h. During addition of oxone, the pH is controlled and regulated (∼8.5−9) by addition of a solution of 1 M K2CO3. The reaction is immediately quenched by addition of CH2Cl2(30 mL) and water (10 mL). The mixture is extracted with CH2Cl2(3 × 20 mL), dried over Na2SO4, and analyzed.
(c)Procedure B.A solution (6 mL) of acetic acid (0.5 mL) and 0.1 M aqueous K2CO3(100 mL) is added under stirring to a mixture of 0.8 mmol of methylp-methoxycinnamate6a(0.154 g, 1 equiv) and ketone5a(0.08 mmol, 0.1 equiv or 0.24 mmol, 0.3 equiv) dissolved in dimethoxyethane (DME, 10 mL). The mixture is cooled to the desired temperature and a solution of oxone (0.68 g, 1.1 mmol, 2.8 equiv of oxidant) in distilled water (3.2 mL) is added dropwise over 8 h. During addition of oxone, the pH is controlled and regulated (∼8.5−9) by addition of a solution of 1.4 M K2CO3. The reaction is immediately quenched by adding CH2Cl2(30 mL) and water (10 mL). The mixture is extracted with CH2Cl2(3 × 20 mL), dried over Na2SO4, and analyzed.
{'key': 'ol0001721b00006/ol0001721b00006_1', 'first-page': '3507', 'volume': '3501', 'author': 'Stilbene IR', 'year': '1997', 'journal-title': 'J. Chem. Soc., Perkin Trans. 1'} / J. Chem. Soc., Perkin Trans. 1 by Stilbene IR (1997)
{'key': 'ol0001721b00008/ol0001721b00008_1', 'first-page': '6298', 'volume': '122', 'author': 'Armstrong A.', 'year': '2000', 'journal-title': 'J. Am. Chem. Soc.'} / J. Am. Chem. Soc. by Armstrong A. (2000)
During these first investigations it was found that the ketones3a,3e,4a,4e, and5edid not undergo Baeyer−Villiger oxidation within the reaction time. They were observed in the correct expected ratio in the1H NMR spectra of the crude products. However, ketone5aunderwent Baeyer−Villiger oxidation at ambient under conditionsAbut was stable at 0 °C under conditionsB. During experiment 8 (procedureA, Table 1) 77% (0.23 mmol) of a 25/75 mixture of5aand the BV-lactones were recovered in the crude product and 50% (0.15 mmol) of a 65/35 mixture of both oxidation products were isolated by chromatography (silica gel, AcOEt/hexane). The1H NMR are consistent with 3-fluoro-6-isopropyl-3-methyloxepan-2-one and 7-fluoro-4-isopropyl-7-methyloxepan-2-one.1H NMR (C6D6, 400 MHz): δ 0.53 (d,J= 7 Hz, 6H, isomer I), 0.55 (d,J= 7 Hz, 3H, isomer II), 0.59 (d,J= 7 Hz, 3H, isomer II), 1−1.7 (m, 6H isomers I and 6H isomer II), 1.29 (d,3JHF= 19 Hz, 3H, isomer II), 1.52 (d,3JHF= 23 Hz, 3H, isomer I), 2.42 (AA‘ part of AA‘XX‘, 2H, isomer II), 3.73 (ddt,2J= 12 Hz,3J= 4 Hz,4J=4J= 2 Hz, 1H, isomer I), 4.35 (dd,2J= 12 Hz,3J= 8.5 Hz, 1H, isomer I).13C NMR (C6D6, 100 MHz): isomer Imajor, δ 19.0, 19.3 (CH3), 25.6 (3JCF= 3.5 Hz, CH2), 26.1 (2JCF= 25 Hz, CH3), 31.3 (CH), 35.4 (2JCF= 26 Hz, CH2), 44.8 (CH), 72.3 (3JCF= 9 Hz, CH2), 97.0 (1JCF= 180 Hz, C), 170.5 (2JCF= 24 Hz, C); isomer IIminor, δ 18.5, 18.7 (CH3), 25.8 (3JCF= 3 Hz, CH2), 28.2 (2JCF= 27 Hz, CH3), 33.5 (CH), 37.1 (2JCF= 26 Hz, CH2), 39.9 (3JCF= 4 Hz, CH2), 40.2 (CH), 113.6 (1JCF= 229 Hz, C), 170.8 (2JCF= 33 Hz, C). IR (CHCl3): ν = 3620, 2960, 2880, 1730, 1440, 1390, 1320 cm-1.
{'key': 'ol0001721b00011/ol0001721b00011_1', 'first-page': '648', 'volume': '41', 'author': 'For R', 'year': '1993', 'journal-title': 'Chem. Pharm. Bull.'} / Chem. Pharm. Bull. by For R (1993)
{'key': 'ol0001721b00012/ol0001721b00012_1', 'first-page': '2509', 'volume': '44', 'author': 'For S', 'year': '1979', 'journal-title': 'J. Org. Chem.'} / J. Org. Chem. by For S (1979)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 2:06 a.m.)
Deposited	3 years, 11 months ago (Sept. 24, 2021, 12:35 a.m.)
Indexed	3 months, 2 weeks ago (May 9, 2025, 12:34 p.m.)
Issued	24 years, 10 months ago (Oct. 24, 2000)
Published	24 years, 10 months ago (Oct. 24, 2000)
Published Online	24 years, 10 months ago (Oct. 24, 2000)
Published Print	24 years, 9 months ago (Nov. 1, 2000)

Funders 0

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BibTeX

@article{Solladi_Cavallo_2000, title={Epoxidation of p-Methoxycinnamates Using Chiral Dioxiranes Derived from New Trisubstituted Halogenated Cyclohexanones: Enhanced Efficiency of Ketones Having an Axial Halogen}, volume={2}, ISSN={1523-7052}, url={http://dx.doi.org/10.1021/ol0001721}, DOI={10.1021/ol0001721}, number={23}, journal={Organic Letters}, publisher={American Chemical Society (ACS)}, author={Solladié-Cavallo, A. and Bouérat, L.}, year={2000}, month=oct, pages={3531–3534} }

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      "unstructured": "(c)Procedure B.A solution (6 mL) of acetic acid (0.5 mL) and 0.1 M aqueous K2CO3(100 mL) is added under stirring to a mixture of 0.8 mmol of methylp-methoxycinnamate6a(0.154 g, 1 equiv) and ketone5a(0.08 mmol, 0.1 equiv or 0.24 mmol, 0.3 equiv) dissolved in dimethoxyethane (DME, 10 mL). The mixture is cooled to the desired temperature and a solution of oxone (0.68 g, 1.1 mmol, 2.8 equiv of oxidant) in distilled water (3.2 mL) is added dropwise over 8 h. During addition of oxone, the pH is controlled and regulated (\u223c8.5\u22129) by addition of a solution of 1.4 M K2CO3. The reaction is immediately quenched by adding CH2Cl2(30 mL) and water (10 mL). The mixture is extracted with CH2Cl2(3 \u00d7 20 mL), dried over Na2SO4, and analyzed."
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      "unstructured": "During these first investigations it was found that the ketones3a,3e,4a,4e, and5edid not undergo Baeyer\u2212Villiger oxidation within the reaction time. They were observed in the correct expected ratio in the1H NMR spectra of the crude products. However, ketone5aunderwent Baeyer\u2212Villiger oxidation at ambient under conditionsAbut was stable at 0 \u00b0C under conditionsB. During experiment 8 (procedureA, Table 1) 77% (0.23 mmol) of a 25/75 mixture of5aand the BV-lactones were recovered in the crude product and 50% (0.15 mmol) of a 65/35 mixture of both oxidation products were isolated by chromatography (silica gel, AcOEt/hexane). The1H NMR are consistent with 3-fluoro-6-isopropyl-3-methyloxepan-2-one and 7-fluoro-4-isopropyl-7-methyloxepan-2-one.1H NMR (C6D6, 400 MHz): \u03b4 0.53 (d,J= 7 Hz, 6H, isomer I), 0.55 (d,J= 7 Hz, 3H, isomer II), 0.59 (d,J= 7 Hz, 3H, isomer II), 1\u22121.7 (m, 6H isomers I and 6H isomer II), 1.29 (d,3JHF= 19 Hz, 3H, isomer II), 1.52 (d,3JHF= 23 Hz, 3H, isomer I), 2.42 (AA\u2018 part of AA\u2018XX\u2018, 2H, isomer II), 3.73 (ddt,2J= 12 Hz,3J= 4 Hz,4J=4J= 2 Hz, 1H, isomer I), 4.35 (dd,2J= 12 Hz,3J= 8.5 Hz, 1H, isomer I).13C NMR (C6D6, 100 MHz): isomer Imajor, \u03b4 19.0, 19.3 (CH3), 25.6 (3JCF= 3.5 Hz, CH2), 26.1 (2JCF= 25 Hz, CH3), 31.3 (CH), 35.4 (2JCF= 26 Hz, CH2), 44.8 (CH), 72.3 (3JCF= 9 Hz, CH2), 97.0 (1JCF= 180 Hz, C), 170.5 (2JCF= 24 Hz, C); isomer IIminor, \u03b4 18.5, 18.7 (CH3), 25.8 (3JCF= 3 Hz, CH2), 28.2 (2JCF= 27 Hz, CH3), 33.5 (CH), 37.1 (2JCF= 26 Hz, CH2), 39.9 (3JCF= 4 Hz, CH2), 40.2 (CH), 113.6 (1JCF= 229 Hz, C), 170.8 (2JCF= 33 Hz, C). IR (CHCl3): \u03bd = 3620, 2960, 2880, 1730, 1440, 1390, 1320 cm-1."
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