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Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization
Author(s) -
Nguyen TuanAnh,
Roger Julien,
Nasrallah Houssein,
Rampazzi Vincent,
Fournier Sophie,
Cattey Hélène,
Sosa Carrizo E. Daiann,
FleuratLessard Paul,
Devillers Charles H.,
Pirio Nadine,
Lucas Dominique,
Hierso JeanCyrille
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202000579
Subject(s) - cycloisomerization , enyne , chemistry , cycloaddition , diphosphines , cationic polymerization , selectivity , medicinal chemistry , ferrocene , catalysis , stereochemistry , organic chemistry , electrode , electrochemistry
Di‐ tert ‐butylated‐bis(phosphino)ferrocene ligands bearing phosphino substituents R ( R=phenyl, cyclohexyl, iso‐propyl, mesityl, or furyl ) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear two‐coordinate, but also rare mononuclear trigonal three‐coordinate and tetrahedral four‐coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X‐ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold‐catalysed cycloisomerization. Cationic linear digold(I) bis(dicyclohexylphosphino) ferrocenes outperform other catalysts in the demanding regioselective cycloisomerization of enyne sulphonamides into cyclohexadienes. Conversely, tetrahedral and trigonal cationic monogold(I) complexes were found incompetent for enyne cycloaddition. We used the two‐coordinate linear electron‐rich Au(I) complex 2 b ( R =Cy) to extend the scope of selective intramolecular cycloaddition of different 1,6‐enyne sulfonylamines with high activity and excellent selectivity to the endo cyclohexadiene products.