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Volumn 11, Issue 15, 2009, Pages 3410-3413

Sml2-promoted intramolecular asymmetric pinacol-type ketone-tert-butanesulfinyl lmine reductive coupling: Stereoselectivity and mechanism

Author keywords

[No Author keywords available]

Indexed keywords

AMINOALCOHOL; IMINE; KETONE;

EID: 68149141338     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol901296u     Document Type: Article
Times cited : (22)

References (54)
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  • 2
    • 68149151038 scopus 로고    scopus 로고
    • DOI: 10.1016/ j.tet.2009.06.003
    • (b) Burchak, O. N.; Py, S. Tetrahedron 2009, DOI: 10.1016/ j.tet.2009.06.003.
    • (2009) Tetrahedron
    • Burchak, O.N.1    Py, S.2
  • 5
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    • Representative examples: (a) Evans, J. W.; Ellman, J. A. J. Org. Chem. 2003, 68, 9948.
  • 10
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    • 2-mediated synthesis, see: (a) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
    • 2-mediated synthesis, see: (a) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
  • 19
    • 0033547940 scopus 로고    scopus 로고
    • For an asymmetric coupling of planar chiral substrates via a bis-ketyl radical mechanism, see
    • (c) Machrouhi, F.; Namy, J.-L. Tetrahedron Lett. 1999, 40, 1315. For an asymmetric coupling of planar chiral substrates via a bis-ketyl radical mechanism, see:
    • (1999) Tetrahedron Lett , vol.40 , pp. 1315
    • Machrouhi, F.1    Namy, J.-L.2
  • 20
    • 0033519208 scopus 로고    scopus 로고
    • Taniguchi, N.; Hata, 8T.; Uemura, M. Angew. Chem., Int. Ed. 1999, 38, 1232.
    • (d) Taniguchi, N.; Hata, 8T.; Uemura, M. Angew. Chem., Int. Ed. 1999, 38, 1232.
  • 38
    • 68149085749 scopus 로고    scopus 로고
    • 1H NMR, and the er was determined by chiral HPLC of N-Ac derivatives of 3; see the Supporting Information.
    • 1H NMR, and the er was determined by chiral HPLC of N-Ac derivatives of 3; see the Supporting Information.
  • 39
    • 68149090657 scopus 로고    scopus 로고
    • s, 2S-3a, since the absolute configuration of sulfur was not disturbed during the reaction.
    • s, 2S-3a, since the absolute configuration of sulfur was not disturbed during the reaction.
  • 40
    • 68149086815 scopus 로고    scopus 로고
    • For recent studies on the role of HMPA, see: a
    • For recent studies on the role of HMPA, see: (a) Faran, H.; Hoz, S. Org. Lett. 2008, 70, 865.
    • (2008) Org. Lett , vol.70 , pp. 865
    • Faran, H.1    Hoz, S.2
  • 45
    • 24644499004 scopus 로고    scopus 로고
    • The S-O bond and the nitrogen lone pair of electrons should be anti-periplanar; see: a
    • The S-O bond and the nitrogen lone pair of electrons should be anti-periplanar; see: (a) Ferreira, F.; Audouin, M.; Chemla, F. Chem,-Eur. J. 2005, 77, 5269.
    • (2005) Chem,-Eur. J , vol.77 , pp. 5269
    • Ferreira, F.1    Audouin, M.2    Chemla, F.3
  • 48
    • 85022594998 scopus 로고    scopus 로고
    • Reversibility of carbonyl reduction: (a) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J. Synlett 1992, 943. Reversibility of ring formation:
    • Reversibility of carbonyl reduction: (a) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J. Synlett 1992, 943. Reversibility of ring formation:
  • 50
    • 68149140528 scopus 로고    scopus 로고
    • The tolerance of the R-sulfinyl gauche-interaction in this reaction could be due to the fact that an N-radical might be roughly triagonal (sp 2, similar to its imime precursor; while for polar 1,2-addition to sulfinimines directly yielding a sterically demanding tetrahedral (metallated) N-anion, such R-sulfinyl interaction becomes the determining factor ref 18a, In the latter case, the shift in hybridization state of nitrogen could also affect the conformation of the sulfinyl group
    • 2), similar to its imime precursor; while for polar 1,2-addition to sulfinimines directly yielding a sterically demanding tetrahedral (metallated) N-anion, such R-sulfinyl interaction becomes the determining factor (ref 18a). In the latter case, the shift in hybridization state of nitrogen could also affect the conformation of the sulfinyl group.
  • 51
    • 68149109408 scopus 로고    scopus 로고
    • In most polar additions to sulfinimines, coordination of substrate O/N atoms to metal cation was proposed to explain the observed stereoselectivity. If anionic cyclization mechanism predominated in the present case, chelation of the hydroxyl and the sulfinylamino groups to Sm(III) would afford either the cis- products or the opposite sense of chiral induction.
    • In most polar additions to sulfinimines, coordination of substrate O/N atoms to metal cation was proposed to explain the observed stereoselectivity. If anionic cyclization mechanism predominated in the present case, chelation of the hydroxyl and the sulfinylamino groups to Sm(III) would afford either the cis- products or the opposite sense of chiral induction.
  • 52
    • 68149177706 scopus 로고    scopus 로고
    • n occupied the axial orientation as the result of stereoelectronic effects in cyclic systems (ref 17a), and this does not reflect its bulk relative to R in acyclic systems (OSmLn > R>H).
    • n occupied the axial orientation as the result of stereoelectronic effects in cyclic systems (ref 17a), and this does not reflect its bulk relative to R in acyclic systems (OSmLn > R>H).
  • 54
    • 68149129303 scopus 로고    scopus 로고
    • Its utility in other asymmetric transformations is being probed
    • Its utility in other asymmetric transformations is being probed.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.