Gold versus Palladium: A Regioselective Cycloisomerization of Aromatic Enynes. Issue 17 (14th November 2013)

• Record Type: Journal Article
• Authors: Aziz, Jessy; Frison, Gilles; Le Menez, Patrick; Brion, Jean‐Daniel; Hamze, Abdallah; Alami, Mouad
• Is Part Of: Advanced synthesis & catalysis. Volume 355:Issue 17(2013)
• Page Start: 3425
• Page End: 3436
• Publication Date: 2013-11-14
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201300746
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Aromatic enynes can be transformed into arylnaphthalenes or benzofulvenes depending on the reaction conditions. Under gold(I) catalysis, exclusive or major 6‐<italic>endo</italic>‐<italic>dig</italic> cyclization took place leading to arylnaphthalenes. However, a catalytic system based on palladium iodide/1, 3‐bis(diphenylphosphino)propane, in the presence of cesium carbonate as a base was necessary to furnish exclusively 5‐<italic>exo</italic>‐<italic>dig</italic> cyclization pattern, regardless of the electronic effects of the substituents. In the latter transformation, a mechanistic study (kinetic isotopic effect, density functional theory) involving a CH activation is suggested for the exclusive formation of benzofulvenes.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg4t6scqfm" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>