+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity

Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity

Chemistry 11(10): 3155-3164

The cyclization of differently substituted aryl alkynes with PtII or AuI catalysts proceeds by endo-dig pathways. When AgI was used to generate reactive cationic AuI catalysts, 2H-chromenes dimerize to form cyclobutane derivatives by a AgI-catalyzed process. A DFT study on the cyclization mechanism shows a kinetic and thermodynamic preference for 6-endo-dig versus 5-exo-dig cyclizations in PtII-catalyzed processes. Calculations indicate that although Friedel-Crafts and the cyclopropanation processes via metal cyclopropyl carbenes show very similar activation energies, platinum cyclopropyl carbenes are the stationary points with the lowest energy.

Please choose payment method:

(PDF emailed within 0-6 h: $19.90)

Accession: 049392503

Download citation: RISBibTeXText

PMID: 15779093

DOI: 10.1002/chem.200401069

Related references

The mechanism and regioselectivity of gold(I) or platinum(II) catalyzed intramolecular hydroarylation to pyrrolopyridinones and pyrroloazepinones. Organic and Biomolecular Chemistry 12(42): 8433-8441, 2014

Theoretical Insight into the Mechansim and Origin of Ligand-Controlled Regioselectivity in Homogenous Gold-Catalyzed Intramolecular Hydroarylation of Alkynes. Journal of Organic Chemistry 83(5): 2763-2772, 2018

Mechanism and origins of selectivity in Ru(II)-catalyzed intramolecular (5+2) cycloadditions and ene reactions of vinylcyclopropanes and alkynes from density functional theory. Journal of the American Chemical Society 135(17): 6588-6600, 2013

Reaction of enol ethers with alkynes catalyzed by transition metals: 5-exo-dig versus 6-endo-dig cyclizations via cyclopropyl platinum or gold carbene complexes. Chemistry 9(11): 2627-2635, 2003

Palladium-catalyzed enantioselective intramolecular hydroarylation of alkynes to form axially chiral 4-aryl 2-quinolinones. Angewandte Chemie 50(17): 3963-3967, 2011

Rhodium-catalyzed intramolecular hydroarylation of 1-halo-1-alkynes: regioselective synthesis of semihydrogenated aromatic heterocycles. Chemistry 20(1): 317-322, 2014

Synthesis of fluoranthenes by hydroarylation of alkynes catalyzed by gold(I) or gallium trichloride. Beilstein Journal of Organic Chemistry 7: 1520-1525, 2011

The Au(I)-catalyzed intramolecular hydroarylation of terminal alkynes under mild conditions: application to the synthesis of 2H-chromenes, coumarins, benzofurans, and dihydroquinolines. Journal of Organic Chemistry 74(22): 8901-8903, 2009

Platinum-catalyzed intramolecular asymmetric hydroarylation of unactivated alkenes with indoles. Organic Letters 8(17): 3801-3804, 2006

Gold(I)-catalyzed intramolecular hydroarylation of allenes. Journal of Organic Chemistry 73(6): 2439-2441, 2008

Gold(I) and platinum(II) switch: a post-Ugi intramolecular hydroarylation to pyrrolopyridinones and pyrroloazepinones. Chemical Communications 48(88): 10916, 2012

Platinum-catalyzed intramolecular hydroarylation of allenyl arenes: efficient synthesis of 1,4-dihydronaphthalenes. Organic Letters 12(11): 2570-2573, 2010

Platinum-catalyzed formal Markownikoff's hydroamination/hydroarylation cascade of terminal alkynes assisted by tethered hydroxyl groups. Journal of Organic Chemistry 74(16): 6315-6318, 2009

Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes. Beilstein Journal of Organic Chemistry 7: 1468-1474, 2011

The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes. Journal of the American Chemical Society 128(39): 12785-12793, 2006