Versatile method for the synthesis of 4-substituted 6-methyl-3- oxabicyclo[3.3.1]non-6-ene-1-methanol derivatives: Prins-type cyclization reaction catalyzed by hafnium triflate

Tetrahedron Letters

Volumn 50, Issue 47, 2009, Pages 6462-6465

  Nakamura, Masayuki ^a   Niiyama, Kenji ^a   Yamakawa, Takeru ^a  

^a BANYU PHARMACEUTICAL CO LTD   (Japan)

Author keywords

Catalytic reaction; Hafnium triflate; Oxabicyclo 3.3.1 nonene; Prins type cyclization reaction

Indexed keywords

ACETAL; ALDEHYDE; BENZALDEHYDE; HAFNIUM; METHANOL DERIVATIVE; PYRIDINE;

ARTICLE; CATALYSIS; CATALYST; CYCLIZATION; PRINS CYCLIZATION; REACTION OPTIMIZATION; SYNTHESIS;

EID: 77951194081     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.08.120     Document Type: Article

References (21)

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20. The formation of the acetal 6 was rapidly observed in a few miniatures by TLC, and the desired product was gradually formed.
21. General procedure: To a mixture of diol 3 (103 mg, 0.659 mmol) and aldehyde 4 (0.13 mL, 0.79 mmol) in acetonitrile (3.2 mL) was added hafnium triflate (25.5 mg, 0.033 mmol) at room temperature and the reaction mixture was stirred at room temperature for 14 h. After completion of the reaction as indicated by TLC, the reaction was quenched with satd NaHCO3 aq and the reaction mixture was extracted with ethyl acetate (2 x 10 mL), the combined organics were washed with brine, dried over anhyd Na2SO4, and evaporated. The resulting residue was purified by silica gel chromatography (hexane:ethyl acetate) to give the desired compound (205 mg, 93%) as a colorless solid. Compound 5: 1H NMR (400 MHz, CDCl3) δ: 7.33-7.25 (4H, m), 7.09-7.04 (1H, m), 6.99-6.93 (4H, m), 5.60-5.56 (1H, m), 4.55 (1H, d, J =1.7 Hz), 3.97 (1H, dd, J = 10.7, 2.7 Hz), 3.64 (1H, dd, J = 10.7, 1.5 Hz), 3.40 (2H, s), 2.38-2.34 (1H, m), 2.25-2.17 (1H, m), 2.12-2.04 (1H, m), 1.86-1.80 (1H, m), 1.71-1.65 (1H, m), 1.06-1.03 (3H, m). ESI-MS 337 [M+H]+.