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Volumn , Issue , 2005, Pages 241-262

Rhodium(I)-Catalyzed [4+2] and [4+2+2] Carbocyclizations

Author keywords

Diastereoselective rhodium catalyzed 4+2+2 carbocyclization; Rhodium(I) catalyzed 4+2+2 carbocyclization reactions; Rhodium(I) catalyzed 4+2 carbocyclizations; Rhodium(I) catalyzed carbocyclization reactions; Synthesis of cyclooctanoids

Indexed keywords


EID: 84890609755     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/3527604693.ch12     Document Type: Chapter
Times cited : (14)

References (66)
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    • OPPOLZER, W.Comprehensive Organic Synthesis; TROST, B.M., FLEMING, I., PAQUETTE, L.A., Eds. Pergamon: Oxford, 1991; Vol. 5, p. 315.
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    • 741 and pertinent references therein
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    • For a detailed discussion of the various modes of complexation, as well as additional methods developed for the Diels-Alder reactions see ref. 1(a) and pertinent references therein.
  • 19
    • 33845185652 scopus 로고
    • The first and only intramolecular transition metal-catalyzed reaction developed prior to this discovery was Ni(0)-catalyzed
    • The first and only intramolecular transition metal-catalyzed reaction developed prior to this discovery was Ni(0)-catalyzed: WENDER, P.A.; JENKINS, T. E.J. Am. Chem. Soc. 1989, 222, 6432.
    • (1989) J. Am. Chem. Soc , vol.222 , pp. 6432
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  • 20
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    • The observed stereoselectivity matches that of the corresponding thermal reaction, for which only 20 product was observed after heating to 120°C for 3 days. Additionally, simple acid catalyst effects were ruled out by exposing the starting ether (21)to 0.1 equiv HCl over 1 h under optimized reaction conditions, in the absence of rhodium catalyst. Under these conditions the starting material was recovered unchanged.
  • 21
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    • This intermediate is also often depicted as an η3-type intermediate.
  • 22
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    • Pronounced rate and selectivity enhancements had previously been observed for Ni(0)-catalyzed cyclodimerizations as well as rhodium-catalyzed alkene hydroformylation reactions. For related references see: (Ni)
    • Pronounced rate and selectivity enhancements had previously been observed for Ni(0)-catalyzed cyclodimerizations as well as rhodium-catalyzed alkene hydroformylation reactions. For related references see: (Ni) VAN LEEUWEN, P.W.N.M.; ROOBEEK, CF.Tetrahedron 1981, 37, 1973.
    • (1981) Tetrahedron , vol.37 , pp. 1973
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  • 24
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    • Ph.D. thesis, University of Delaware, Newark, Delaware 19713, or "Recent advances in Rh-catalyzed carbocycli-zation reactions"
    • For a complete and detailed discussion see JOHN.E. ROBINSON, Ph.D. thesis, University of Delaware, Newark, Delaware 19713, or "Recent advances in Rh-catalyzed carbocycli-zation reactions" John E. Robinson, http:// www.chem.wayne.edu/acs-organic-division/fellowships.html.
    • Robinson, J.E.1
  • 26
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    • There are numerous examples of rhoda-cycle-propene type intermediates in the literature, suggesting that the modified Magnus-Buchwald type of transition state may be quite feasible. For lead references see
    • There are numerous examples of rhoda-cycle-propene type intermediates in the literature, suggesting that the modified Magnus-Buchwald type of transition state may be quite feasible. For lead references see: BUCKNER, S.W.; FREISER, B.S.Polyhedron 1989, 8, 1401.
    • (1989) Polyhedron , vol.8 , pp. 1401
    • Buckner, S.W.1    Freiser, B.S.2
  • 36
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    • This general strategy of activating the rho-dium(I) complex through hydrogenation of the dialkene complex was previously utilized by Bosnich and co-workers to enhance the rate of hydroacylation in the corresponding rhodium(I)-catalyzed transformation. For lead references see ref. 15 and pertinent references therein.
  • 37
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    • This catalyst system was also applied to the [5 + 2] carbocyclization reactions, discussed at length in Chapter 13 of this book.
  • 41
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    • Livinghouse and co-workers report a similar carbocyclization, using a dimethyl malonate diene-ene derivative, in which they obtained 6ee(69) with a highly sterically hindered DIOP-based ligand (ref. 25). The unaltered DIOP ligand was also highly efficient (83), but imparted poor enantio- control (10 ee).
  • 42
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    • To date there are more than 100 cyclo-octanoid-containing natural products. For a lead reference concerning this statistic, see
    • To date there are more than 100 cyclo-octanoid-containing natural products. For a lead reference concerning this statistic, see: PETASIS, N.A.; PATANE, M.A.Tetrahedron 1992, 48, 5757.
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  • 43
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    • For recent review of metal-mediated synthesis of cyclooctanoids see
    • For recent review of metal-mediated synthesis of cyclooctanoids see: SIEBURTH, S.MCN.; CUNARD, T.Tetrahedron 1996, 52, 6251.
    • (1996) Tetrahedron , vol.52 , pp. 6251
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    • For lead references concerning the [4+ 4] intermolecular cyclizations see, Academic Press, New York
    • For lead references concerning the [4+ 4] intermolecular cyclizations see: JOLLY, P.W.; WILKE, G.inThe Organic Chemistry of Nickel, Vol. 2. Academic Press, New York, 1975.
    • (1975) The Organic Chemistry of Nickel , vol.2
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    • Other transition metal complexes also catalyzed the dimerization of simple butadiene type substrates. For related examples see
    • Other transition metal complexes also catalyzed the dimerization of simple butadiene type substrates. For related examples see: BOSCH, M.; BROOKHART, M.S.; ILG, K.; WERNER, H.Angew. Chem., Int. Ed. Engl. 2000, 39, 2304.
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    • For lead references on intramolecular [4+ 4] cyclization reactions see
    • For lead references on intramolecular [4+ 4] cyclization reactions see: WENDER, P.A.; IHLE, N.C.J. Am. Chem. Soc. 1986, 208, 4678.
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    • For lead references pertaining to iron- and cobalt-catalyzed [4+ 2 + 2] intermolecular cyclizations see
    • For lead references pertaining to iron- and cobalt-catalyzed [4+ 2 + 2] intermolecular cyclizations see: GRECO, A.; CARBONARO, A.; DALL'ASTA, G.J. Org. Chem. 1970, 35, 271.
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    • and references cited therein
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    • Attempts to assign the relative configuration of the homodimer were complicated due to the extreme instability of the compound. Additionally, due to the increased reactivity of this substrate for homo-dimerization, there was no noticeable concentration effect between 0.1 and 0.0626 M.
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    • For the related use of a temporary sulfur tether in Pauson-Khand reactions see
    • For the related use of a temporary sulfur tether in Pauson-Khand reactions see: CASTRO, J.; MOYANO, A.; PERICAS, M.A.; RIERA, A.J. Org. Chem. 1998, 63, 3346.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.