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Volumn 20, Issue 8, 2001, Pages 1580-1591

Bis(oxazolinyl)phenylrhodium(III) aqua complexes: Synthesis, structure, enantioselective allylation of aldehydes, and mechanistic studies

Author keywords

[No Author keywords available]

Indexed keywords

ASYMMETRIC CATALYSTS; BISOXAZOLINYLPHENYLRHODIUM AQUA COMPLEXES; ENANTIOSELECTIVE ALLYLATION;

EID: 0035897451     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010018y     Document Type: Article
Times cited : (104)

References (100)
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    • Recently, the allylation of aldehydes with allyltributyltin catalyzed with chiral pyrrolidine-derived rhodium(III) complexes was reported, see: (b) Shi, M.; Lei, G.-X.; Masaki, Y. Tetrahedron: Asymmetry 1999, 10, 2071.
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    • note
    • Selected bond distances (Å) and angles (deg) for 5e: Rh(1)-Cl(1) = 2.325(3), Rh(1)-Cl(2) = 2.331(3), Rh(1)-O(3) = 2.291(5), Rh-(1)-N(1) = 2.075(6), Rh(1)-N(2) = 2.082(6), Rh(1)-C(1) = 1.921(7); Cl(1)-Rh(1)-Cl(2) = 175.10(9), Cl(1)-Rh(1)-O(3) = 89.8(3), Cl(1)-Rh(1)-N(1) = 92.3(2), Cl(1)-Rh(1)-N(2) = 86.9(2), Cl(1)-Rh(1)-C(1) = 89.7(4) O(3)-Rh(1)-C(1) = 179.3(5), N(1)-Rh(1)-N(2) = 158.7(2).
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    • note
    • The absolute configuration of anti-7 was determined by the retention time of the chiral HPLC analysis.
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    • The absolute configuration of syn-7 was determined by the retention time of the chiral HPLC analysis using the authentic sample, which was prepared by Roush's method (57% ee, IS, 1R); see: Roush, W. R.; Ando, K.; Powers, D. B.; Palkowits, A. D.; Halterman, R. L. J. Am. Chem. Soc. 1990, 112, 6339.
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  • 77
    • 0011393326 scopus 로고    scopus 로고
    • note
    • Selected bond distances (Å) and angles (deg) for 8: Rh(1)-Cl-(1) = 2.341(4), Rh(1)-Cl(2) = 2.338(4), Rh(1)-O(3) = 2.27(1), Rh(1)-N(1) = 2.06(1), Rh(1)-N(2) = 2.12(1), Rh(1)-C(1) = 1.93(2); Cl(1)-Rh(1)-Cl(2) = 177.9(2), Cl(1)-Rh(1)-O(3) = 91.9(3), Cl(1)-Rh(1)-N(1) = 87.9(4), Cl(1)-Rh(1)-N(2) = 91.2(3), Cl(1)-Rh(1)-C(1) = 92.2(5), O(3)-Rh(1)-C(1) = 173.9(6), N(1)-Rh(1)-N(2) = 160.0(5), Rh-(1)-O(3)-C(15)= 137(1).
  • 79
  • 81
    • 0011437774 scopus 로고    scopus 로고
    • note
    • Setected bond distances (Å) and angles (deg) for 9: Rh(1)-Cl-(1) = 2.334(4), Rh(1)-Cl(2) = 2.340(4), Rh(1)-N(1) = 2.08(1), Rh(1)-N(2) = 2.12(1), Rh(1)-N(3) = 2.24(1), Rh(1)-C(1) = 1.87(1); Cl(1)-Rh-(1)-Cl(2) = 179.1(1), Cl(1)-Rh(1)-N(1) = 92.1(4), Cl(1)-Rh(1)-N(2) = 87.3(3), Cl(1)-Rh(1)-N(3) = 90.8(4), Cl(1)-Rh(1)-C(1) = 89.1(4), N(3)-Rh(1)-C(1) = 177.5(5), N(1)-Rh(1)-N(2) = 161.0(5).
  • 82
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    • note
    • Selected bond distances (Å) and angles (deg) for 10: Rh(1)-C(1) = 1.941(7), Rh(1)-C(19) = 2.106(7), Rh(1)-N(1) = 2.053(5), Rh-(1)-N(2) = 2,055(5), C(19)-N(3) = 1.145(9); N(1)-Rh(1)-N(2) = 157.3(2), Rh(1)-C(19)-N(3) = 170.2(7).
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    • Other examples of anti-selective allylation of aldehydes with γ-substituted (E)-allyltins without chelation or transmetalation were reported. One of the anti-selective allylations was only preceded by the use of aryl-substituted allyltins. The authors explained that these observations were due to a chairlike cyclic transition state; see: (a) Koreeda, M.; Tanaka, Y. Chem. Lett. 1982, 1299.
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    • Another case was the use of the γ-substituted (E)-allyltins with a bulky substituent such as the tert-butyl or trialkylsilyl group at the β-position. This reaction was assumed to proceed via the inverse antiperiplanar acyclic transition state as in our case; see: (c) Nishigaichi, Y.; Ishida, N.; Nishida, M.; Takuwa, A. Tetrahedron Lett. 1996, 37, 3701.
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