메뉴 건너뛰기




Volumn 15, Issue 32, 2009, Pages 7846-7849

Asymmetrie iminium ion catalysis with a novel bifunctional primary amine thiourea: Controlling adjacent quaternary and tertiary stereocenters

Author keywords

Asymmetric catalysis; Chirality; Conjugate addition; Primary amine; Thioureas

Indexed keywords

ASYMMETRIC CATALYSIS; ASYMMETRIC CONJUGATE ADDITION; BENZOIC ACID; BIFUNCTIONAL; C-C BONDS; CATALYST LOADINGS; CATALYTIC PERFORMANCE; CINNAMALDEHYDE; CONJUGATE ADDITION; ENANTIOCONTROL; IMINIUM; ORGANIC SYNTHESIS; OXINDOLES; PRIMARY AMINE; PRIMARY AMINES; STARTING MATERIALS; TERTIARY STEREOCENTERS;

EID: 68349101812     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200802466     Document Type: Article
Times cited : (162)

References (70)
  • 1
    • 55049138759 scopus 로고    scopus 로고
    • For recent reviews, see: a, Ed, P. I. Dalko, Wiley-VCH, Weinheim
    • For recent reviews, see: a) Enantioselective Organocatalysis (Ed.: P. I. Dalko), Wiley-VCH, Weinheim, 2007;
    • (2007) Enantioselective Organocatalysis
  • 4
    • 52149113820 scopus 로고    scopus 로고
    • for a commentary on the advent of asymmetric organocatalysis, see: c
    • for a commentary on the advent of asymmetric organocatalysis, see: c) D. W. C. MacMillan, Nature 2008, 455, 304.
    • (2008) Nature , vol.455 , pp. 304
    • MacMillan, D.W.C.1
  • 5
    • 0034748990 scopus 로고    scopus 로고
    • For recent reviews on aminocatalysis, see: a
    • For recent reviews on aminocatalysis, see: a) B. List, Synlett 2001, 1687;
    • (2001) Synlett , pp. 1687
    • List, B.1
  • 6
    • 68349095644 scopus 로고    scopus 로고
    • P. Melchiorre, M. Marigo, A. Carlone, G.. Bartoli, Angew. Chem. 2008, 120, 6232;
    • b) P. Melchiorre, M. Marigo, A. Carlone, G.. Bartoli, Angew. Chem. 2008, 120, 6232;
  • 8
    • 38349100690 scopus 로고    scopus 로고
    • for a review on iminium catalysis, see: for a review on enamine catalysis, see: c
    • for a review on enamine catalysis, see: c) S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471; for a review on iminium catalysis, see:
    • (2007) Chem. Rev , vol.107 , pp. 5471
    • Mukherjee, S.1    Yang, J.W.2    Hoffmann, S.3    List, B.4
  • 9
    • 33745715054 scopus 로고    scopus 로고
    • for a seminal paper on dienamine catalysis, see
    • d) G. Leiais, D.W.C. MacMillan, Aldrichimica Acta 2006, 39, 79; for a seminal paper on dienamine catalysis, see:
    • (2006) Aldrichimica Acta , vol.39 , pp. 79
    • Leiais, G.1    MacMillan, D.W.C.2
  • 15
    • 0037419866 scopus 로고    scopus 로고
    • Only two examples of iminium-catalyzed conjugate addition of prochiral nucleophiles to enals with high diastereoselectivity (7 to 24:1 dr) have been reported: a) S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192;
    • Only two examples of iminium-catalyzed conjugate addition of prochiral nucleophiles to enals with high diastereoselectivity (7 to 24:1 dr) have been reported: a) S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192;
  • 19
    • 68349117739 scopus 로고    scopus 로고
    • For recent examples of low diastereoselective, albeit highly enantioselective, conjugate additions to enals promoted by III through ¡minium activation, see: a D. A. Alonso, S. Kitagaki, N. Utsumi, C. F. Barbas III, Angew. Chem. 2008, 120, 4664;
    • For recent examples of low diastereoselective, albeit highly enantioselective, conjugate additions to enals promoted by III through ¡minium activation, see: a) D. A. Alonso, S. Kitagaki, N. Utsumi, C. F. Barbas III, Angew. Chem. 2008, 120, 4664;
  • 27
    • 58249120495 scopus 로고    scopus 로고
    • For recent examples on the use of chiral primary amine thiourea catalysts in enamine activation, see, a
    • For recent examples on the use of chiral primary amine thiourea catalysts in enamine activation, see : a) D. A. Yalalov, S. B. Tsogoeva, T. E. Shubina, I. M. Martynova, T. Clark, Angew. Chem. 2008, 120, 6726;
    • (2008) Angew. Chem , vol.120 , pp. 6726
    • Yalalov, D.A.1    Tsogoeva, S.B.2    Shubina, T.E.3    Martynova, I.M.4    Clark, T.5
  • 35
    • 53849084173 scopus 로고    scopus 로고
    • For recent cinchona alkaloid catalyzed asymmetric aldol-type reactions of oxindoles, providing contiguous quaternary stereocenters, see: a
    • For recent cinchona alkaloid catalyzed asymmetric aldol-type reactions of oxindoles, providing contiguous quaternary stereocenters, see: a) S. Ogawa, N. Shibata, J. Inagaki, S. Nakamura, T. Toru, M. Shiro, Angew. Chem. 2007, 119, 8820;
    • (2007) Angew. Chem , vol.119 , pp. 8820
    • Ogawa, S.1    Shibata, N.2    Inagaki, J.3    Nakamura, S.4    Toru, T.5    Shiro, M.6
  • 36
    • 36549020091 scopus 로고    scopus 로고
    • 8666; for asymmetric catalytic transformations by using oxindoles as the nucleophile, see
    • Angew. Chem. Int. Ed. 2007, 46, 8666; for asymmetric catalytic transformations by using oxindoles as the nucleophile, see:
    • (2007) Angew. Chem. Int. Ed , vol.46
  • 50
    • 68349115450 scopus 로고    scopus 로고
    • For meaningful examples of the potential of chiral primary amines derived from cinchona alkaloids in iminium activation of enones, see: a J.-W. Xie, W. Chen, R. Li, M. Zeng, W. Du, L. Yue, Y.-C. Chen, Y. Wu, J. Zhu, J.-G. Deng, Angew. Chem. 2007, 119, 393;
    • For meaningful examples of the potential of chiral primary amines derived from cinchona alkaloids in iminium activation of enones, see: a) J.-W. Xie, W. Chen, R. Li, M. Zeng, W. Du, L. Yue, Y.-C. Chen, Y. Wu, J. Zhu, J.-G. Deng, Angew. Chem. 2007, 119, 393;
  • 58
    • 55249110210 scopus 로고    scopus 로고
    • for recent reviews, see
    • Angew. Chem. Int. Ed. 2008, 47, 8703; for recent reviews, see:
    • (2008) Angew. Chem. Int. Ed , vol.47 , pp. 8703
  • 61
    • 23044486704 scopus 로고    scopus 로고
    • To the best of our knowledge, chiral primary amines have not yet been used for the iminium activation of α,ß-unsaturated aldehydes; they have proven to be effective for the iminium activation of enones (see reference [10]) and of α-substituted acroleins, see: a) K. Ishihara, K. Nakano, J. Am. Chem. Soc. 2005, 127, 10504;
    • To the best of our knowledge, chiral primary amines have not yet been used for the iminium activation of α,ß-unsaturated aldehydes; they have proven to be effective for the iminium activation of enones (see reference [10]) and of α-substituted acroleins, see: a) K. Ishihara, K. Nakano, J. Am. Chem. Soc. 2005, 127, 10504;
  • 64
    • 68349108975 scopus 로고    scopus 로고
    • Both enantiomers of Via are easily accessible from a single-step synthesis, see the Supporting Information.
    • Both enantiomers of Via are easily accessible from a single-step synthesis, see the Supporting Information.
  • 65
    • 68349106245 scopus 로고    scopus 로고
    • It is likely that the acid serves to facilitate catalyst turnover by promoting iminium formation/imine hydrolysis; for similar effects with primary amine thiourea catalysts in enamine catalysis, see references [7b, c
    • It is likely that the acid serves to facilitate catalyst turnover by promoting iminium formation/imine hydrolysis; for similar effects with primary amine thiourea catalysts in enamine catalysis, see references [7b, c].
  • 66
    • 68349113100 scopus 로고    scopus 로고
    • 2 = Cl) led to a decreased stereoselectivity in the reaction with 2a (1.5:1 dr; 11 % ee).
    • 2 = Cl) led to a decreased stereoselectivity in the reaction with 2a (1.5:1 dr; 11 % ee).
  • 67
    • 84877935319 scopus 로고    scopus 로고
    • These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • CCDC-710802 (4) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data-request/cif
    • CCDC-710802 (4) contains the supplementary crystallographic data for this paper
  • 68
    • 68349094466 scopus 로고    scopus 로고
    • 2) in the catalyst scaffold led to a complete loss of catalytic activity and this evidence ruled out possible activation of the nucleophile through chiral Brønsted base catalysis.
    • 2) in the catalyst scaffold led to a complete loss of catalytic activity and this evidence ruled out possible activation of the nucleophile through chiral Brønsted base catalysis.
  • 69
    • 68349096769 scopus 로고    scopus 로고
    • The employment of the N-Boc protected oxindole under the best reaction conditions afforded low stereocontrol, albeit with improved reactivity (18 h; >95% conversion; 2:1 dr; 67% ee).
    • The employment of the N-Boc protected oxindole under the best reaction conditions afforded low stereocontrol, albeit with improved reactivity (18 h; >95% conversion; 2:1 dr; 67% ee).
  • 70
    • 68349110110 scopus 로고    scopus 로고
    • The presence of the primary amine is crucial for the catalytic activity, see reference [16]; at this stage of the investigations a plausible Brønsted acid activation of unsaturated aldehydes cannot be ruled out.
    • The presence of the primary amine is crucial for the catalytic activity, see reference [16]; at this stage of the investigations a plausible Brønsted acid activation of unsaturated aldehydes cannot be ruled out.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.