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Tetrahedron Letters
Volumn 56, Issue 23, 2015, Pages 3120-3122
Total synthesis of clavosolide A via tandem allylic oxidation/oxa-conjugate addition reaction
Author keywords

Clavosolide; gem Disubstituent effect; Oxa conjugate addition; Tandem reaction; Tetrahydropyran; Total synthesis
Indexed keywords

CLAVOSOLIDE A; ESTER; MACROLIDE; UNCLASSIFIED DRUG;
EID: 84929961118     PISSN: 00404039     EISSN: 18733581     Source Type: Journal    
DOI: 10.1016/j.tetlet.2014.11.135     Document Type: Article
Times cited : (9)
References (26)
  • 22
    • 84929958684 scopus 로고    scopus 로고
    • Compound 4: To a solution of diol 5 (117 mg, 0.24 mmol) in CH2Cl2 (4 mL, 0.06 M) at 25°C was added MnO2 (89 mg, 1.02 mmol). The resulting solution was stirred at 25°C for 1 h. Additional equivalents of MnO2 (89 mg, 1.02 mmol) were added every hour for 4 h. The reaction mixture was then treated with a mixture of dimethyltriazolium iodide (5 mg, 0.022 mmol, 9 mol %), DBU (410 μL, 1 M solution in CH2Cl2), MnO2 (89 mg, 1.02 mmol), MeOH (400 μL), and MS 4 Å (585 mg, 500 wt %). The resulting mixture was stirred for 12 h. The crude mixture was then filtered through a small plug of celite and concentrated in vacuo. The crude mixture was purified by column chromatography (silica gel, hexanes/EtOAc, 5:1) to provide 2,3-trans-2,6-cis-tetrahydropyran methyl ester 4 (104 mg, 0.20 mmol) in 84% as a clear oil; 1H NMR (500 MHz, CDCl3) δ 5.56 (dddd, J = 15.5, 8.5, 8.5, 8.5 Hz, 1H), 5.39 (ddd, J = 15.0, 8.5, 1.5 Hz, 1H), 4.31 (ddd, J = 8.5, 8.5, 4.0 Hz, 1H), 3.89 (ddd, J = 9.5, 9.5, 3.0 Hz, 1H), 3.81 (dddd, J = 9.5, 9.5, 3.5, 1.5 Hz, 1H), 3.68 (s, 3H), 3.12 (ddd, J = 15.0, 12.5, 3.0 Hz, 1H), 2.89 (ddd, J = 15.0, 12.5, 3.0 Hz, 1H), 2.59-2.68 (m, 3H), 2.54 (dd, J = 14.5, 3.0 Hz, 1H), 2.31 (dd, J = 14.5, 9.5 Hz, 1H), 2.07-2.10 (m, 1H), 1.78-1.86 (m, 2H), 1.73 (dd, J = 13.5, 10.5 Hz, 1H), 1.70 (dd, J = 6.0, 1.5 Hz, 3H), 1.64 (dd, J = 10.0, 7.0 Hz, 1H), 1.50 (ddd, J = 13.0, 9.0, 3.5 Hz, 1H), 1.14 (d, J = 7.0 Hz, 3H), 1.04 (s, 21H); 13C NMR (125 MHz, CDCl3) δ 172.0, 134.2, 125.9, 73.9, 71.0, 70.6, 54.9, 51.7, 45.7, 44.3, 43.8, 39.7, 25.88, 25.83, 25.2, 18.24, 18.21, 17.8, 12.5.
    • Compound 4: To a solution of diol 5 (117 mg, 0.24 mmol) in CH2Cl2 (4 mL, 0.06 M) at 25°C was added MnO2 (89 mg, 1.02 mmol). The resulting solution was stirred at 25°C for 1 h. Additional equivalents of MnO2 (89 mg, 1.02 mmol) were added every hour for 4 h. The reaction mixture was then treated with a mixture of dimethyltriazolium iodide (5 mg, 0.022 mmol, 9 mol %), DBU (410 μL, 1 M solution in CH2Cl2), MnO2 (89 mg, 1.02 mmol), MeOH (400 μL), and MS 4 Å (585 mg, 500 wt %). The resulting mixture was stirred for 12 h. The crude mixture was then filtered through a small plug of celite and concentrated in vacuo. The crude mixture was purified by column chromatography (silica gel, hexanes/EtOAc, 5:1) to provide 2,3-trans-2,6-cis-tetrahydropyran methyl ester 4 (104 mg, 0.20 mmol) in 84% as a clear oil; 1H NMR (500 MHz, CDCl3) δ 5.56 (dddd, J = 15.5, 8.5, 8.5, 8.5 Hz, 1H), 5.39 (ddd, J = 15.0, 8.5, 1.5 Hz, 1H), 4.31 (ddd, J = 8.5, 8.5, 4.0 Hz, 1H), 3.89 (ddd, J = 9.5, 9.5, 3.0 Hz, 1H), 3.81 (dddd, J = 9.5, 9.5, 3.5, 1.5 Hz, 1H), 3.68 (s, 3H), 3.12 (ddd, J = 15.0, 12.5, 3.0 Hz, 1H), 2.89 (ddd, J = 15.0, 12.5, 3.0 Hz, 1H), 2.59-2.68 (m, 3H), 2.54 (dd, J = 14.5, 3.0 Hz, 1H), 2.31 (dd, J = 14.5, 9.5 Hz, 1H), 2.07-2.10 (m, 1H), 1.78-1.86 (m, 2H), 1.73 (dd, J = 13.5, 10.5 Hz, 1H), 1.70 (dd, J = 6.0, 1.5 Hz, 3H), 1.64 (dd, J = 10.0, 7.0 Hz, 1H), 1.50 (ddd, J = 13.0, 9.0, 3.5 Hz, 1H), 1.14 (d, J = 7.0 Hz, 3H), 1.04 (s, 21H); 13C NMR (125 MHz, CDCl3) δ 172.0, 134.2, 125.9, 73.9, 71.0, 70.6, 54.9, 51.7, 45.7, 44.3, 43.8, 39.7, 25.88, 25.83, 25.2, 18.24, 18.21, 17.8, 12.5.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.