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Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters : an experimental and theoretical study

(2009) CHEMISTRY-A EUROPEAN JOURNAL. 15(13). p.3243-3260
Author
Organization
Abstract
Experimental and theoretical studies on Au- and Pt-catalyzed cycloisomerization of a branched dienyne with an acetate group at the propargylic position are presented. The peculiar architecture of the dienyne precursor, which has both a 1,6- and a 1,5-enyne skeleton, leads, in the presence of alkynophilic gold catalysts, to mixtures of bicyclic compounds 3, 4, and 5. Formation of unprecedented bicyclo[3.1.0]hexene 5 is the main focus of this study. The effect of the ancillary ligand on the gold center was examined and found to be crucial for formation of 5. Further mechanistic studies, involving cyclization of an enantioenriched dienyne precursor, O-18-labeling experiments, and DFT calculations, allowed an unprecedented reaction pathway to be proposed. We show that bicyclo[3.1.0]hexene 5 is likely formed by a 1,3-OAc shift/allene-ene cyclization/1,2-OAc shift sequence, as calculated by DFT and supported by Au-catalyzed cyclization of isolated allenenyl acetate 7, which leads to improved selectivity in the formation of 5. Additionally, the possibility of OAc migration from allenyl acetates was supported by a trapping experiment with styrene that afforded the corresponding cyclopropane derivative. This unprecedented generation of a vinyl metal carbene from an allenyl ester supports a facile enynyl ester/allenenyl ester equilibrium. Further examination of the difference in reactivity between enynyl acetates and their corresponding [3,3]-rearranged allenenyl acetates toward Au- and Pt-catalyzed cycloisomerization is also presented.
Keywords
alkynes, allenes, cycloisomerization, density functional calculations, gold, GAUSSIAN-BASIS SETS, PROPARGYLIC ESTERS, STRUCTURAL-CHARACTERIZATION, EFFICIENT FORMATION, ADDITION-REACTIONS, TRANSITION-METALS, ATOM ECONOMY, AB-INITIO, C-C, PTCL2-MEDIATED CYCLOISOMERIZATION

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MLA
Marion, Nicolas, et al. “Gold- and Platinum-Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters : An Experimental and Theoretical Study.” CHEMISTRY-A EUROPEAN JOURNAL, vol. 15, no. 13, 2009, pp. 3243–60.
APA
Marion, N., Lemiere, G., Correa, A., Costabile, C., Ramon, R. S., Moreau, X., … Nolan, S. (2009). Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters : an experimental and theoretical study. CHEMISTRY-A EUROPEAN JOURNAL, 15(13), 3243–3260.
Chicago author-date
Marion, Nicolas, Gilles Lemiere, Andrea Correa, Chiara Costabile, Ruben S Ramon, Xavier Moreau, Pierre de Fremont, et al. 2009. “Gold- and Platinum-Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters : An Experimental and Theoretical Study.” CHEMISTRY-A EUROPEAN JOURNAL 15 (13): 3243–60.
Chicago author-date (all authors)
Marion, Nicolas, Gilles Lemiere, Andrea Correa, Chiara Costabile, Ruben S Ramon, Xavier Moreau, Pierre de Fremont, Rim Dahmane, Alexandra Hours, Denis Lesage, Jean-Claude Tabet, Jean-Philippe Goddard, Vincent Gandon, Luigi Cavallo, Louis Fensterbank, Max Malacria, and Steven Nolan. 2009. “Gold- and Platinum-Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters : An Experimental and Theoretical Study.” CHEMISTRY-A EUROPEAN JOURNAL 15 (13): 3243–3260.
Vancouver
1.
Marion N, Lemiere G, Correa A, Costabile C, Ramon RS, Moreau X, et al. Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters : an experimental and theoretical study. CHEMISTRY-A EUROPEAN JOURNAL. 2009;15(13):3243–60.
IEEE
[1]
N. Marion et al., “Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters : an experimental and theoretical study,” CHEMISTRY-A EUROPEAN JOURNAL, vol. 15, no. 13, pp. 3243–3260, 2009.
@article{8169529,
  abstract     = {Experimental and theoretical studies on Au- and Pt-catalyzed cycloisomerization of a branched dienyne with an acetate group at the propargylic position are presented. The peculiar architecture of the dienyne precursor, which has both a 1,6- and a 1,5-enyne skeleton, leads, in the presence of alkynophilic gold catalysts, to mixtures of bicyclic compounds 3, 4, and 5. Formation of unprecedented bicyclo[3.1.0]hexene 5 is the main focus of this study. The effect of the ancillary ligand on the gold center was examined and found to be crucial for formation of 5. Further mechanistic studies, involving cyclization of an enantioenriched dienyne precursor, O-18-labeling experiments, and DFT calculations, allowed an unprecedented reaction pathway to be proposed. We show that bicyclo[3.1.0]hexene 5 is likely formed by a 1,3-OAc shift/allene-ene cyclization/1,2-OAc shift sequence, as calculated by DFT and supported by Au-catalyzed cyclization of isolated allenenyl acetate 7, which leads to improved selectivity in the formation of 5. Additionally, the possibility of OAc migration from allenyl acetates was supported by a trapping experiment with styrene that afforded the corresponding cyclopropane derivative. This unprecedented generation of a vinyl metal carbene from an allenyl ester supports a facile enynyl ester/allenenyl ester equilibrium. Further examination of the difference in reactivity between enynyl acetates and their corresponding [3,3]-rearranged allenenyl acetates toward Au- and Pt-catalyzed cycloisomerization is also presented.},
  author       = {Marion, Nicolas and Lemiere, Gilles and Correa, Andrea and Costabile, Chiara and Ramon, Ruben S and Moreau, Xavier and de Fremont, Pierre and Dahmane, Rim and Hours, Alexandra and Lesage, Denis and Tabet, Jean-Claude and Goddard, Jean-Philippe and Gandon, Vincent and Cavallo, Luigi and Fensterbank, Louis and Malacria, Max and Nolan, Steven},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keywords     = {alkynes,allenes,cycloisomerization,density functional calculations,gold,GAUSSIAN-BASIS SETS,PROPARGYLIC ESTERS,STRUCTURAL-CHARACTERIZATION,EFFICIENT FORMATION,ADDITION-REACTIONS,TRANSITION-METALS,ATOM ECONOMY,AB-INITIO,C-C,PTCL2-MEDIATED CYCLOISOMERIZATION},
  language     = {eng},
  number       = {13},
  pages        = {3243--3260},
  title        = {Gold- and platinum-catalyzed cycloisomerization of enynyl esters versus allenenyl esters : an experimental and theoretical study},
  url          = {http://dx.doi.org/10.1002/chem.200801387},
  volume       = {15},
  year         = {2009},
}

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