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Volumn , Issue , 2005, Pages 357-377

Cyclopentane Construction by Rhodium(II)-Mediated Intramolecular C-H Insertion

Author keywords

Comparing and contrasting rhodium catalysts; Computational approach; Cyclization versus elimination; Cyclopentane construction by rhodium(II) mediated intramolecular C H insertion; Design of an enantioselective catalyst

Indexed keywords


EID: 84890769366     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/3527604693.ch16     Document Type: Chapter
Times cited : (17)

References (48)
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    • For an alternative synthesis of astrogorgiadiol from vitamin D, see
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    • For general reviews of rhodium mediated C-H insertions, PATTENDEN G., Ed., PERGAMON PRESS: OXFORD
    • For general reviews of rhodium mediated C-H insertions, see TABER, D.F.Comprehensive Organic Synthesis; PATTENDEN G., Ed., PERGAMON PRESS: OXFORD, 1991; Vol. 3, pp. 1045-1062.
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    • Alternatively, the initial complex of the electron-deficient carbon with the electron density in the target C-H could be depicted as a three-center, two-electron bond (ref. 9). We initially took this approach computationally, but found that the results did not correlate with the diastereoselectivity observed for the reaction. More recent computational work by Nakamura has confirmed the four-center nature of the transition state for Rh-mediated C-H insertion
    • Alternatively, the initial complex of the electron-deficient carbon with the electron density in the target C-H could be depicted as a three-center, two-electron bond (ref. 9). We initially took this approach computationally, but found that the results did not correlate with the diastereoselectivity observed for the reaction. More recent computational work by Nakamura has confirmed the four-center nature of the transition state for Rh-mediated C-H insertion: NAKAMURA, E.; YOSHIKAI, N.; YAMANAKA, M.J. Am. Chem. Soc. 2002, 224, 7181.
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    • Mechanics and ZINDO were used as implemented on the Tektronix CAChe workstation. Although our initial work (ref. 6) included minimizing the Rh-Rh core with ZINDO, we have subsequently found that this approach works just as well with Mechanics alone. The CAChe workstation is particularly well suited to the sort of analysis outlined here, as its superb three-dimensional visualization facilitates understanding of the competing transition states.
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    • Rhodium pivalate {dirhodium tetrakisf(2, 2-dimethylpropanato-O: O')]} was synthesized by heating commercially available rhodium trifluoroacetate in 8 equiv pivalic acid for 24 h followed by removal of excess acid by heating under vacuum. The crude catalyst was purified by flash chromatogra phy using an MTBE/petroleum ether gradient. TLC Rf (10 MTBE/petroleum ether) = 0.52. For leading references to the preparation of other rhodium carboxylates, see
    • f (10 MTBE/petroleum ether) = 0.52. For leading references to the preparation of other rhodium carboxylates, see FELTHOUSE, T. R.Prog. Inorg. Chem. 1982, 29, 73.
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    • For the development of DOSP by Davies, see
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    • For the development of BiTISP by Davies, see
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    • Tetrakis(carboxylato)dimetal complexes have been prepared from Cr, Cu, Mo, Re, Rh, Ru, Tc, and W. For leading references, see, John Wiley and Sons: New York
    • Tetrakis(carboxylato)dimetal complexes have been prepared from Cr, Cu, Mo, Re, Rh, Ru, Tc, and W. For leading references, see COTTON, F.A.; WALTON, R.A.Multiple Bonds Between Metal Atoms; John Wiley and Sons: New York, 1982.
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    • Chisholm has reported diacids that can connect two tungsten (or molybdenum) dimers, to make tetramers
    • Chisholm has reported diacids that can connect two tungsten (or molybdenum) dimers, to make tetramers: CAYTON, R. H.; CHISHOLM, M.H.; HUFFMAN, J.C.; LOBKOVSKY, E. B.J. Am. Chem. Soc.1991, 223, 8709.
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    • Diacid was prepared by coupling a-a'-di-bromo-m-xylene with allylmagnesium chloride, followed by RuO4-mediated cleavage of the resultant diene [29]. Diacid , prepared by an alternative route, was already a known compound:
    • Diacid was prepared by coupling a-a'-di-bromo-m-xylene with allylmagnesium chloride, followed by RuO4-mediated cleavage of the resultant diene [29]. Diacid , prepared by an alternative route, was already a known compound: RUGGLI, P.; BUCHELER, P. Helv. Chim. Acta 1947, 30, 2048.
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    • For the application of this push-pull stabilization principle to intermolecular C-H insertion, see
    • For the application of this push-pull stabilization principle to intermolecular C-H insertion, see DAVIES. H.M.L.; HANSEN, T.J. Am. Chem. Soc. 1997, 229, 9075.
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    • Davies, H.M.L.1    Hansen, T.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.