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Synlett
Volumn , Issue 11, 2008, Pages 1627-1630
A novel route towards the synthesis of spirocyclic bislactones
Author keywords

Bislactones; Dianion synthon; Lithiation; Spirocyclization; Trimethylenemethane
Indexed keywords

1,7 DIOXASPIRO[4.4]NONANE 2,6 DIONE; ACYCLIC TRIMETHYLENEMETHANE DIANION SYNTHON; LACTONE DERIVATIVE; METHANE; NONANE;
EID: 48249153849     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1078489     Document Type: Article
Times cited : (8)
References (47)
  • 1
    • 0032801086 scopus 로고    scopus 로고
    • For a microreview, see
    • For a microreview, see: Wong, H. N. C. Eur. J. Org. Chem. 1999, 1757.
    • (1999) Eur. J. Org. Chem , pp. 1757
    • Wong, H.N.C.1
  • 15
    • 0010528037 scopus 로고
    • For some total syntheses, see: a
    • For some total syntheses, see: (a) Poss, A. J. Tetrahedron Lett. 1987, 28, 5469.
    • (1987) Tetrahedron Lett , vol.28 , pp. 5469
    • Poss, A.J.1
  • 38
    • 0034904455 scopus 로고    scopus 로고
    • For reviews, see: a
    • For reviews, see: (a) Yus, M. Synlett 2001, 1197.
    • (2001) Synlett , pp. 1197
    • Yus, M.1
  • 41
    • 48249095850 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Compounds 3 A solution of 2-chloromethyl-3-(2-methoxyethoxy)propene (164 mg, 1 mmol) and the corresponding ketone (0.95 mmol) in THF (2 mL, was added over 1.5 h to a green suspension of lithium powder (50 mg, 7 mmol) and DTBB (27 mg, 0.1 mmol) in THF (3 mL) at -78 °C. The mixture was allowed to reach 0 °C and then neat 2-(2-iodoethoxy)tetrahydro-2H-pyran27 (1.5 mmol) was added over 1.5 h continuing the stirring for 2 h at r.t. The reaction mixture was hydrolyzed with H2O (5 mL, extracted with EtOAc (3×10 mL, and the organic phase was dried over anhyd MgSO4. After removal of the solvent under reduced pressure (210-2 bar, the resulting residue was purified by column chromatography (SiO2, hexane-EtOAc) to yield compounds 3. l-[2-Methylidene-5-(tetrahydro-2H-pyran-2-yloxy)pentyl] cyclohexanol (3b) Colorless oil; Rf= 0.53 hexane-EtOAc, 4:1
    • 3: 270.2195; found: 270.2201.
  • 42
    • 48249100416 scopus 로고    scopus 로고
    • 19g
    • 19g
  • 43
    • 48249140561 scopus 로고    scopus 로고
    • General Procedure for the Deprotection of Compounds 3 A flake of PTSA was added to a solution of the protected alcohol 3 (1 mmol) in MeOH (5 mL, After stirring for 1 h, the volatiles were removed under vacuum (2.10-2 bar, and H2O (10 mL) was added to the residue followed by extraction with EtOAc (3×10 mL, The organic phase was dried over anhyd MgSO4 and the solvent evaporated under reduced pressure to give the pure product 4 which did not require further purification. 1-(5-Hydroxy-2-methylidenepentyl)cyclohexanol (4b) Colorless oil; Rf= 0.40 (hexane-EtOAc, 4:1, IR (neat, 3373 (OH, 3072, 1638 (C=CH, 1146, 1059 cm-1 (CO, 1H NMR (300 MHz, CDCl 3, δ, 1.40-1.70 [m, 10 H, CH2)5, 1.72-1.80 (m, 2 H, CH2CH2OH, 2.10-2.20 (m, 6 H, 2 × OH, 2 × CH2C=CH2, 3.65 t, J
    • 2O]: 180.1514; found: 180.1515.
  • 44
    • 48249153310 scopus 로고    scopus 로고
    • General Procedure for the Cyclization of Compounds 4 Iodine (0.382 g, 1.5 mmol) was added to a solution of the corresponding diol 4 (1 mmol) in THF (5 mL, The mixture was stirred for 5 min at r.t. and then Ag 2O (0.346 g, 1.5 mmol) was added with additional stirring for 24 h. The resulting suspension was filtered and H2O (10 mL) was added to the filtrate, followed by extraction with EtOAc (3×10 mL, The organic phase was successively washed with a sat. solution of Na2SO 3 (2 × 10 mL) and H2O (2 × 10 mL, and dried over anhyd MgSO4. The solvent was removed under reduced pressure to furnish pure compounds 5. 1,13-Dioxaspiro [4.1.5.2] tetradecane (5b) Colorless oil; Rf= 0.69 (hexane-EtOAc, 4:1, IR (neat, 1058 cm-1 (CO, 1H NMR (300 MHz CDCl 3):δ=1.30-1.95: [m, 14 H, CH2)5, CH2C
    • 2: 196.1463; found: 196.1467.
  • 45
    • 48249149060 scopus 로고    scopus 로고
    • 1,13-Dioxaspiro[4.1.5.2]tetradecane-2,14-dione (6b) A suspension of RuO2 (21 mg, 0.16 mmol) and NaIO4 (1.04 g, 4.88 mmol) in H2O (5 mL) was added to a solution of the l,7-dioxaspiro[4.4] nonane 5b (1.0 mmol) in CC14 (5 mL) at r.t.28 After stirring the reaction for 24 h, i-PrOH (3 mL) was added, and the resulting mixture was extracted with CCl4 (2 × 5 mL, The organic layer was dried over anhyd MgSO4, filtered, and evaporated under reduced pressure. The resulting residue was passed through a pad containing Celite in order to eliminate the remaining ruthenium compounds, yielding the corresponding pure spirocyclic bislactone 6b, which did not require any further purification. Colorless solid; mp 138-140 °C; R f= 0.50 (hexane-EtOAc, 4:1, IR (KBr, 1768 (C=0, 1139 cm -1 (CO, 1H NMR (300 MHz, CDCl3, δ, 1.30-2.65 m, 16 H, 8
    • -1; F(000) = 240; T= 24 ± 1 °C; CCDC number 679641 contains the supplementary crystallographic data for compound 6b. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.ac.uk/data_request/cif.
  • 46
    • 0018416699 scopus 로고    scopus 로고
    • 2 at 0-25 °C for 1.25 h, following a standard literature procedure: Bernady, K. F.; Floyd, M. B.; Poletto, J. F.; Weiss, M. J. J. Org. Chem. 1979, 44, 1438.
  • 47
    • 0001297928 scopus 로고
    • For some applications of this oxidation system, see for instance
    • For some applications of this oxidation system, see for instance: Berkowitz, W. F.; Perumattam, J.; Amarasekara, A. J. Org. Chem. 1987, 52, 1119.
    • (1987) J. Org. Chem , vol.52 , pp. 1119
    • Berkowitz, W.F.1    Perumattam, J.2    Amarasekara, A.3

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.