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Volumn , Issue 13, 2007, Pages 2025-2028

A catalytic synthesis of aziridines without the usual byproducts

Author keywords

Catalysis; Diazo compounds; Heterocycles; Imines; Lewis acids

Indexed keywords

AZIRIDINE DERIVATIVE; CARBENE; CARBOXYLIC ACID DERIVATIVE; CIS AZIRIDINE 2 CARBOXYLIC ACID; DIAZOMETHANE; DIMER; ESTER; IMINE; LEWIS ACID; PHENYLDIAZOMETHANE; UNCLASSIFIED DRUG;

EID: 34548182854     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-984872     Document Type: Article
Times cited : (18)

References (67)
  • 1
  • 11
    • 34548188977 scopus 로고    scopus 로고
    • Jacobsen, E. N, Pfaltz, A, Yamamoto, H, Eds, Springer: New York, Chap. 17
    • (c) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H., Eds.; Springer: New York, 1999, Chap. 17.
    • (1999) Comprehensive Asymmetric Catalysis
    • Jacobsen, E.N.1
  • 52
    • 24044524181 scopus 로고    scopus 로고
    • For recent progress in the development of potential carbene-forming catalysts that suppress diazo coupling, see: (a) Fructos, M. R, Belderrain, T. R, de Frémont, P, Scott, N. M, Nolan, S. P, Díaz-Requejo, M. M, Pérez, P. J. Angew. Chem. Int. Ed. 2005, 44, 5284
    • For recent progress in the development of potential carbene-forming catalysts that suppress diazo coupling, see: (a) Fructos, M. R.; Belderrain, T. R.; de Frémont, P.; Scott, N. M.; Nolan, S. P.; Díaz-Requejo, M. M.; Pérez, P. J. Angew. Chem. Int. Ed. 2005, 44, 5284.
  • 56
    • 34548171187 scopus 로고    scopus 로고
    • A couple catalytic aziridine-forming reactions of α-imino esters have been reported but none employ aryldiazomethanes, see references 4h and 4x
    • A couple catalytic aziridine-forming reactions of α-imino esters have been reported but none employ aryldiazomethanes, see references 4h and 4x.
  • 57
    • 34548161121 scopus 로고    scopus 로고
    • Phenyldiazomethane was synthesized according to literature procedure: Creary, X. Org. Synth. 1986, 64, 207.
    • (a) Phenyldiazomethane was synthesized according to literature procedure: Creary, X. Org. Synth. 1986, 64, 207.
  • 58
    • 18144398606 scopus 로고    scopus 로고
    • Aryldiazomethanes are not commercially available and there have been several reports of explosions related to use of these substances. Encouraging developments have been recently reported for the in situ generation of aryldiazomethane compounds, see: Fulton, J. R, Aggarwal, V. K, de Vicente, J, Chem. 2005, 1479
    • (b) Aryldiazomethanes are not commercially available and there have been several reports of explosions related to use of these substances. Encouraging developments have been recently reported for the in situ generation of aryldiazomethane compounds, see: Fulton, J. R.; Aggarwal, V. K.; de Vicente, J. Eur. J. Org. Chem. 2005, 1479.
  • 59
    • 34548172940 scopus 로고    scopus 로고
    • 2O, 0.33 M 4 in toluene at -80°C). For polymerizations of 4, see: Bawn, C. E. H.; Ledwith, A.; Matthies, P. J. Polym. Sci. 1958, 33, 21.
    • 2O, 0.33 M 4 in toluene at -80°C). For polymerizations of 4, see: Bawn, C. E. H.; Ledwith, A.; Matthies, P. J. Polym. Sci. 1958, 33, 21.
  • 61
    • 34548147007 scopus 로고    scopus 로고
    • The protic acid, TfOH, was recently found to be an effective catalyst for aziridine formation of imines with diazo acetates, see reference 4h.
    • The protic acid, TfOH, was recently found to be an effective catalyst for aziridine formation of imines with diazo acetates, see reference 4h.
  • 62
    • 34548161383 scopus 로고    scopus 로고
    • 3 use 10 mol%, presumably due to no optimization, see references: 4e, 4l, 4r, 4w, 4x, 4z, and 5c.
    • 3 use 10 mol%, presumably due to no optimization, see references: 4e, 4l, 4r, 4w, 4x, 4z, and 5c.
  • 63
    • 34548174664 scopus 로고    scopus 로고
    • The only other report of a highly active Lewis acid catalyst in the synthesis of aziridines from imines with any diazo compound involves use of SnCl4 0.05 mol% for 50% conversion in 50 min, see reference 5a
    • 4 (0.05 mol% for 50% conversion in 50 min), see reference 5a.
  • 64
    • 34548189461 scopus 로고    scopus 로고
    • In these cases, an insufficient level of Lewis acid is present to selectively decompose the trans-aziridine isomer, as has been reported in reference 4m
    • In these cases, an insufficient level of Lewis acid is present to selectively decompose the trans-aziridine isomer, as has been reported in reference 4m.
  • 65
    • 0033525459 scopus 로고    scopus 로고
    • Bravo, P.; Capelli, S.; Crucianelli, M.; Guidetti, M.; Markovsky, A. L.; Meille, S. V.; Soloshonok, V. A.; Sorochinsky, A. E.; Viani, F.; Zanda, M. Tetrahedron 1999, 55, 3025.
    • Bravo, P.; Capelli, S.; Crucianelli, M.; Guidetti, M.; Markovsky, A. L.; Meille, S. V.; Soloshonok, V. A.; Sorochinsky, A. E.; Viani, F.; Zanda, M. Tetrahedron 1999, 55, 3025.
  • 66
    • 34548180800 scopus 로고    scopus 로고
    • Typical Synthetic Procedure: To a CH2Cl2 solution (5 mL) of imine 3 (216 mg, 1.04 mmol) at -78°C was added BF3·Et2O (5 mol, 6.5 μL, 52 μmol) and the solution was stirred at -78°C for 15 min. To this pale yellow solution was added, all at once, 4 (1.1 equiv, 327 μL of 3.5 M 4 in CH 2Cl2) and stirring was continued for 1.5 h at -78°C. The reaction flask was then removed from the -78°C bath and stirring was continued for another 45 min during which time the reaction mixture came to r.t. The reaction mixture was diluted with CH2Cl2 (5 mL, washed with a sat. aq solution of NaHCO3 (3 x 10 mL, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to provide a yellow oil that was purified on silica gel by flash column chromatography using PE-EtOAc (from 95:5 to 85:15) to provide pure cis
    • 5f (269.7 mg, 87%) as an off-white solid.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.