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Synlett 2012; 23(13): 1947-1949
DOI: 10.1055/s-0032-1316705
DOI: 10.1055/s-0032-1316705
letter
Ti(Oi-Pr)4-Promoted Regio- and Stereoselective Aminolysis of 2,3-Epoxy Amides
Authors
Weitere Informationen
Publikationsverlauf
Received: 18. April 2012
Accepted after revision: 14. Juni 2012
Publikationsdatum:
26. Juli 2012 (online)
Abstract
A mild and inexpensive Ti(Oi-Pr)4-mediated aminolysis of 2,3-epoxy amides has been developed. The reaction proceeds with excellent regioselectivity, regardless of the steric hindrance of the substituents on the heterocyclic ring, providing vicinal amino alcohols that are very suitable for synthetic applications.
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References and Notes
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- 13 HPLC analysis was performed with a VYDAC reverse-phase C18 column (25 cm by 4.6 mm); MeCN–H2O containing 0.1% TFA, 25:75 to 35:65; flow rate: 1.0 mL; UV detection: 254 nm
- 14 General procedure: A mixture of 2,3-epoxy amide (1 mmol), amine (excess, 1 mL), and Ti(Oi-Pr)4 (1.5 mmol) was stirred at the required temperature for 12 h. After this time, EtOAc was added and the organic phase was washed with aqueous tartaric acid solution (0.5 M), dried over Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel column chromatography (CH2Cl2–MeOH, 95:5, 0.2% NH4OH). Compound 3: 1H NMR (300 MHz, CDCl3): δ = 0.80–0.95 (m, 9 H), 1.15–1.65 (m, 12 H), 2.21–2.67 (m, 4 H), 2.74–2.85 (m, 1 H), 3.76–3.85 (m, 2 H), 3.89 (d, J = 7.1 Hz, 1 H), 4.59 (br s, 1 H), 5.04–5.20 (m, 2 H), 5.69–5.85 (m, 1 H), 7.80 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 13.9, 20.5, 21.2, 27.5, 31.4, 41.5, 51.1, 63.6, 68.8, 116.5, 133.9, 173.4. Compound 8: 1H NMR (300 MHz, CDCl3): δ = 0.83 (t, J = 6.6 Hz, 3 H), 1.11–1.81 (m, 10 H), 2.34–2.51 (m, 2 H), 2.54–2.76 (m, 3 H), 3.76–3.84 (m, 2 H), 3.88 (d, J = 7.1 Hz, 1 H), 4.30 (br s, 1 H), 5.01–5.22 (m, 2 H), 5.67–5.86 (m, 1 H), 8.10 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 14.1, 21.2, 24.3, 26.5, 27.8, 41.3, 50.5, 67.4, 68.6, 116.1, 133.9, 173.48. Compound 9: 1H NMR (300 MHz, CDCl3): δ = 0.85 (t, J = 7.1 Hz, 3 H), 1.31–1.81 (m, 4 H), 2.53–2.63 (m, 2 H), 2.64–2.76 (m, 3 H), 3.57–3.76 (m, 5 H), 3.86–3.91 (m, 2 H), 4.11 (d, J = 7.15 Hz, 1 H), 5.10–5.23 (m, 2 H), 5.74–5.91 (m, 1 H), 7.65 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 14.2, 20.9, 27.8, 41.5, 50.0, 66.8, 67.4, 69.1, 116.5, 133.8, 173.4. Compound 10: 1H NMR (300 MHz, CDCl3): δ = 0.85–0.97 (m, 6 H), 1.21–1.65 (m, 12 H), 2.21–2.67 (m, 3 H), 2.91–3.05 (m, 1 H), 3.78–3.85 (m, 2 H), 4.01 (d, J = 7.2 Hz, 1 H), 4.21 (br s, 1 H), 5.04–5.20 (m, 2 H), 5.69–5.85 (m, 1 H), 7.69 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 13.9, 17.9, 20.3, 21.2, 23.1, 27.5, 31.0, 41.2, 53.1, 56.8, 69.8, 116.3, 133.9, 172.4. Compound 11: 1H NMR (300 MHz, CDCl3): δ = 0.74–2.02 (m, 17 H), 2.41–2.56 (m, 1 H), 3.06–3.22 (m, 2 H), 3.79–3.98 (m, 2 H), 4.01–4.07 (m, 1 H), 5.06–5.24 (m, 2 H), 5.73–5.87 (m, 1 H), 7.21 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 13.9, 19.1, 24.9, 25.0, 31.0, 33.5, 34.3, 41.0, 53.9, 56.4, 71.3, 116.1, 133.9, 172.1. Compound 12: 1H NMR (300 MHz, CDCl3): δ = 0.87 (t, J = 7.1 Hz, 3 H), 1.24–1.57 (m, 4 H), 3.72–3.99 (m, 4 H), 4.28 (d, J = 1.6 Hz, 1 H), 5.04–5.27 (m, 2 H), 5.66–5.88 (m, 1 H), 6.57–6.78 (m, 3 H), 6.93–7.07 (br s, 1 H), 7.07–7.21 (m, 3 H). 13C NMR (75.4 MHz, CDCl3): δ = 14.2, 19.7, 31.6, 33.9, 41.3, 41.6, 55.5, 72.3, 113.8, 116.8, 117.5, 129.6, 133.9, 147.3, 172.7. Compound 13: 1H NMR (300 MHz, CDCl3): δ = 0.85–0.95 (m, 9 H), 1.21–1.65 (m, 12 H), 2.20–2.65 (m, 4 H), 2.79 (d, J = 2.1 Hz, 3 H), 2.81–2.95 (m, 2 H), 3.91 (d, J = 7.2 Hz, 1 H), 6.09 (br s, 1 H). 13C NMR (75.4 MHz, CDCl3): δ = 13.9, 20.4, 21.1, 25.7, 27.4, 31.4, 41.5, 63.6, 68.8, 173.4. Compound 14: 1H NMR (300 MHz, CDCl3): δ = 0.82–0.95 (m, 9 H), 1.15–1.67 (m, 12 H), 2.23–2.65 (m, 4 H), 2.73–2.83 (m, 1 H), 3.91 (d, J = 7.1 Hz, 1 H), 4.39 (d, J = 14.5 Hz, 1 H), 4.42 (d, J = 14.5 Hz, 1 H), 4.62 (br s, 1 H), 6.39 (br s, 1 H), 7.05–7.37 (m, 5 H). 13C NMR (75.4 MHz, CDCl3): δ = 13.9, 20.5, 21.2, 27.5, 31.4, 41.5, 55.4, 63.6, 68.8, 139.7, 128.5, 128.1, 126.8, 168.2. Compound 20: 1H NMR (300 MHz, CDCl3): δ = 0.84–1.97 (m, 13 H), 3.10–3.24 (m, 1 H), 3.76–4.12 (m, 4 H), 4.65 (d, J = 5.6 Hz, 1 H), 5.05–5.33 (m, 2 H), 5.76–5.94 (m, 1 H), 6.76 (br s, 1 H), 7.08–7.68 (m, 5 H). 13C NMR (75.4 MHz, CDCl3): δ = 26.0, 26.2, 28.4, 29.5, 30.2, 41.3, 47.1, 51.4, 63.9, 70.2, 116.3, 126.8, 128.1, 128.4, 130.6, 134.3, 175.0