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Volumn 11, Issue 17, 2005, Pages 5086-5093

From solution-phase to solid-phase enyne metathesis: Crossover in the relative performance of two commonly used ruthenium pre-catalysts

Author keywords

Annulation; Diversityoriented synthesis; Homogeneous catalysis; Metathesis; Solid phase synthesis

Indexed keywords

CATALYSIS; ESTERS; SOLUTIONS; SUBSTRATES; SYNTHESIS (CHEMICAL);

EID: 24344500852     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200500279     Document Type: Article
Times cited : (12)

References (69)
  • 9
    • 1842483218 scopus 로고    scopus 로고
    • For recent reviews on enyne metathesis, see: a) S. T. Diver, A. J. Giessert, Chem. Rev. 2004, 104, 1317;
    • (2004) Chem. Rev. , vol.104 , pp. 1317
    • Diver, S.T.1    Giessert, A.J.2
  • 19
    • 0003008165 scopus 로고    scopus 로고
    • For examples of the effects of changing linker length and constitution on reaction outcome in 1% DVB polystyrene, see: a) B. Yan, Q. Sun, J. Org. Chem. 1998, 63, 55;
    • (1998) J. Org. Chem. , vol.63 , pp. 55
    • Yan, B.1    Sun, Q.2
  • 23
    • 24344444420 scopus 로고    scopus 로고
    • note
    • Initial intermolecular enyne metathesis, involving equilibration to a double-bond geometry that permits formation of a potentially thermodynamically more stable product containing a six-membered cyclic boronic ester, has not been ruled out. However, the failure to generate more than trace amounts of the desired cyclic dialkenylboronic ester when the pinacol alkynylboronic ester was used in place of the diisopropyl boronic ester in a solution phase enyne metathesis reaction suggests that this pathway is less significant.
  • 28
    • 24344484690 scopus 로고    scopus 로고
    • (Eds.: K. C. Nicolaou, R. Hanko, W. Hartwig), Wiley-VCH, Weinheim
    • For recent descriptions of solid phase olefin metathesis, see: a) F. Zaragoza in Handbook of Combinatorial Chemistry. Vol. 1 (Eds.: K. C. Nicolaou, R. Hanko, W. Hartwig), Wiley-VCH, Weinheim, 2002, p. 595;
    • (2002) Handbook of Combinatorial Chemistry , vol.1 , pp. 595
    • Zaragoza, F.1
  • 45
    • 33644994354 scopus 로고
    • A high degree of site separation exists in regular 1% DVB cross-linked polystyrene resins but, due to the dynamic nature of the matrix, at least some amount of transient site interaction always occurs, see ref. [11a]. For an early account of site-site interactions, sec: H. Rapoport, J. I. Crowley. Acc. Chem. Res. 1976, 9, 135.
    • (1976) Acc. Chem. Res. , vol.9 , pp. 135
    • Rapoport, H.1    Crowley, J.I.2
  • 46
    • 24344491112 scopus 로고    scopus 로고
    • note
    • Although the homoallylic alcohols are all part of the same polymeric molecule, reaction with another support-bound substrate will still be referred to as intermolecular.
  • 53
    • 24344499520 scopus 로고    scopus 로고
    • note
    • 1H MAS-NMR.
  • 54
    • 0037716294 scopus 로고    scopus 로고
    • Various copper salts have also been shown to aid metathesis reactions, (see: M. Rivard, S. Blechert, Eur. J. Org. Chem. 2003, 2225) but these offered no significant improvements in this case.
    • (2003) Eur. J. Org. Chem. , pp. 2225
    • Rivard, M.1    Blechert, S.2
  • 56
    • 24344498262 scopus 로고    scopus 로고
    • note
    • It may be hypothesized that under these conditions, a propagating carbene would be very similar to that generated when catalyst 3 is used as the pre-catalyst.
  • 64
    • 24344476242 scopus 로고    scopus 로고
    • See http://www.synphase.com for details.
  • 65
    • 24344503714 scopus 로고    scopus 로고
    • note
    • Although substrate concentrations vary between solid and solutionphase reactions, these results show that substrate concentration is not believed to be a contributory factor in the crossover phenomenon. Additionally, running solution-phase experiments under more concentrated conditions (0.5-1 M relative to homoallylic alcohol) did not effect the trend, with catalyst 3 being superior in these cases.
  • 69
    • 24344499747 scopus 로고    scopus 로고
    • note
    • Examples of metathesis reactions in which facilitating the release of ruthenium may prove helpful include: enyne metathesis, ring-opening metathesis (ROM), and tandem ring closing/ring-opening metathesis (RCM/ROM).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.