Dissecting Anion Effects in Gold(I)‐Catalyzed Intermolecular Cycloadditions. Issue 1 (13th January 2014)

• Record Type: Journal Article
• Authors: Homs, Anna; Obradors, Carla; Lebœuf, David; Echavarren, Antonio M.
• Is Part Of: Advanced synthesis & catalysis. Volume 356:Issue 1(2014)
• Page Start: 221
• Page End: 228
• Publication Date: 2014-01-13
• 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.201300704
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>From a series of gold complexes of the type [<italic>t‐</italic>BuXPhosAu(MeCN)]X (X=anion), the best results in intermolecular gold(I)‐catalyzed reactions are obtained with the complex with the bulky and soft anion BAr₄^F− [BAr₄^F−=3, 5‐bis(trifluoromethyl)phenylborate] improving the original protocols by 10–30% yield. A kinetic study on the [2+2] cycloaddition reaction of alkynes with alkenes is consistent with an scenario in which the rate‐determining step is the ligand exchange to generate the (η²‐phenylacetylene)gold(I) complex. We have studied in detail the subtle differences that can be attributed to the anion in this formation, which result in a substantial decrease in the formation of unproductive σ, π‐(alkyne)digold(I) complexes by destabilizing the conjugated acid formed.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg4sm4904w" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>