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Synlett
Volumn , Issue 14, 2007, Pages 2298-2300
Aldol reactions in water using a β-cyclodextrin-binding proline derivative
Author keywords

cyclodextrin; Adamantane; Aldol reaction; Organocatalysis; Proline
Indexed keywords

ALDEHYDE DERIVATIVE; BETA CYCLODEXTRIN; CYCLOHEXANONE; PROLINE DERIVATIVE; WATER;
EID: 34548790076     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-985569     Document Type: Article
Times cited : (43)
References (39)
  • 22
    • 31444456557 scopus 로고    scopus 로고
    • Mase, N.; Nakai, Y.; Ohara, N.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas, C. F. III J. Am. Chem. Soc. 2006, 128, 734.
    • (a) Mase, N.; Nakai, Y.; Ohara, N.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas, C. F. III J. Am. Chem. Soc. 2006, 128, 734.
  • 23
    • 33646142092 scopus 로고    scopus 로고
    • Mase, N.; Watanabe, K.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas, C. F. III J. Am. Chem. Soc. 2006, 128, 4966.
    • (b) Mase, N.; Watanabe, K.; Yoda, H.; Takabe, K.; Tanaka, F.; Barbas, C. F. III J. Am. Chem. Soc. 2006, 128, 4966.
  • 33
    • 34548806412 scopus 로고    scopus 로고
    • Synthesis of 6 To a solution of 5 (70.8 mg, 0.2 mmol) in CH2Cl2 (1 mL) was added solid 1-adamantane carboxylic acid chloride 4 (44 mg, 0.22 mmol) at 0°C, followed by addition of DIPEA (52 mg, 0.4 mmol, The reaction mixture was stirred for 4 h at r.t. and finally diluted with CH2Cl2 (5 mL, The organic phase was washed consecutively with 1 N HCl, H2O, brine and dried over Na 2SO4. The solvent was removed under reduced pressure. Purification of the residue by flash chromatography using hexane-EtOAc (2:1) affords 6 as an oil (96 mg, 93, α]D25 -32.1 (c 0.88, CHCl3, 1H NMR (400 MHz, CDCl 3, δ, 7.23-7.37 (m, 10 H, 6.65 (d, 1 H, J, 9.2 Hz, 4.95-5.34 (m, 4 H, 4.69 (m, 1 H, 4.41-150 (m, 1 H, 3.51-3.71 (m, 2 H, 2.41-2.50 (m, 1 H, 2.00 (m, 3 H, 1.91 (m, 1 H, 1.63-1.73 m, 12 H, 13C
    • 5: C, 72.07; H, 7.02; N, 5.42. Found: C, 71.27; H, 7.09; N, 5.20.
  • 34
    • 34548719281 scopus 로고    scopus 로고
    • Synthesis of 1 To a solution of compound 6 (96 mg, 0.186 mmol) in MeOH (2 mL) was added 10% Pd/C (30 mg, The reaction mixture was stirred for 5 h under hydrogen, subsequently filtered through Celite and the catalyst was washed with MeOH three times. The combined organic solutions were concentrated under reduced pressure to afford the proline derivative 1 as a colorless solid (54 mg, 100, mp 230-232°C; [α]D 25 -32.9 (c 0.5, MeOH, 1H NMR (400 MHz, DMSO-d6, δ, 7.60 (d, 1 H, J, 6.8 Hz, 4.34 (m, 1 H, 4.15 (t, 1 H, J, 8.4 Hz, 3.28 (dd, 1 H, J, 11.2, 7.2 Hz, 3.10 (dd, 1 H, J, 11.2, 6.0 Hz, 2.46 (m, 1 H, 1.91 (m, 4 H, 1.58-1.72 (m, 12 H, 13C NMR (100 MHz, DMSO-d6, δ, 177.93, 170.99, 58.99, 49.98, 48.50, 39.30, 36.94, 34.67, 28.43. ESI-MS: m/z, 293.4 [M, 1, Anal. Calcd, ) for C 16H
    • 3: C, 65.73; H, 8.27; N, 9.58. Found: C, 65.66; H, 8.18; N, 9.44.
  • 35
    • 34548799703 scopus 로고    scopus 로고
    • 2O): δ = 180.7 (NHC=O), 174.3 (COOH), 102.7 (C-1′), 81.9 (C-4′), 73.5 (C-3′), 72.4 (C-2′), 72.3 (C-5′), 60.6 (C-α), 60.5 (C-6′), 50.4 (C-δ), 49.2 (C-γ), 40.9 (C-1), 38.9 (C-2), 36.8 (C-4), 34.8 (C-β), 27.8 (C-3).
    • 2O): δ = 180.7 (NHC=O), 174.3 (COOH), 102.7 (C-1′), 81.9 (C-4′), 73.5 (C-3′), 72.4 (C-2′), 72.3 (C-5′), 60.6 (C-α), 60.5 (C-6′), 50.4 (C-δ), 49.2 (C-γ), 40.9 (C-1), 38.9 (C-2), 36.8 (C-4), 34.8 (C-β), 27.8 (C-3).
  • 37
    • 34548727390 scopus 로고    scopus 로고
    • 2O using a mixing time of 500 ms and 512 (142 ms) and 2048 (285 ms) points (acquisition times) in the F1 and the F2 dimension. Assignment of the resonances of this complex was accomplished using standard COSY, HMQC, and HMBC pulse sequences. NMR data were processed using Bruker XWINNMR software.
    • 2O using a mixing time of 500 ms and 512 (142 ms) and 2048 (285 ms) points (acquisition times) in the F1 and the F2 dimension. Assignment of the resonances of this complex was accomplished using standard COSY, HMQC, and HMBC pulse sequences. NMR data were processed using Bruker XWINNMR software.
  • 38
    • 34548790110 scopus 로고    scopus 로고
    • General Procedure for the Aldol Reaction Catalyzed by the Inclusion Complex of 1 and β-Cyclodextrin 2 To a suspension of the proline derivative 1 (5.84 mg, 0.02 mmol) in H2O (0.2 mL) was added β-cyclodextrin 2 (22.7 mg, 0.02 mmol) and stirred for 10 min at r.t. until a clear solution was obtained; then cyclohexanone (80 μL, 0.8 mmol) was added. The reaction mixture was stirred at r.t. for further 10 min and subsequently aldehyde 7 (0.2 mol) was added. The reaction mixture was stirred for 3-96 h (TLC monitoring the consumption of aldehyde, The reaction was quenched with aq NH4Cl and extracted with EtOAc. The combined organic layers were washed with H2O and brine, dried over Na 2SO4. Purification by flash chromatography (silica gel, hexane-EtOAc, 2:1) gave the pure aldol products for further analysis. For Recycle Case After the completion of reaction, the reaction mixture was directly
    • 2 under reduced pressure.
  • 39
    • 34548749211 scopus 로고    scopus 로고
    • Absolute configuration of the aldol products anti-9 were determined by optical rotation in comparison to reported values6 except compound 9h. The following are the analytical data of 2-hydroxymethylene-(2′,6′-dichlorophenyl) cyclohexanone (9h, anti-9h: 1H NMR (400 MHz, CDCl3, δ, 7.29 (m, 2 H, 7.13 (m, 1 H, 5.82 (dd, 1 H, J, 9.6, 4.4 Hz, 3.67 (d, 1 H, J, 4.4 Hz, 3.46-3.49 (m, 1 H, 2.35-2.52 (m, 2 H, 2.05-2.09 (m, 1 H, 1.78-1.82 (m, 1 H, 1.62-1.69 (m, 2 H, 1.49-1.53 (m, 1 H, 1.34-1.41 (m, 1 H, 13C NMR (100 MHz, CDCl3, δ, 214.85, 136.08, 135.10, 129.92, 70.97, 54.04, 42.85, 30.26, 28.04, 25.10. ESI-MS: m/z, 295.3 (100, M, Na, The ee of anti-9h (97, was determined by HPLC with a Chiralpak AD-H column heptane-2-PrOH, 90:10, 20°C, 210 nm, 0.5 mL/min; major enantiomer tR, 24.2
    • R = 22.1 min.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.