Dialkylbiphenylphosphane-Au(I) complexes exhibit only weak metal-arene interactions with the covering arene ring. However, the contacts in isoleptic Ag(I) and Cu(I) complexes are shorter than the limiting values of 3.03 A (Ag(I)) and 2.83 A (Cu(I)). Strong metal-arene interactions were also found in the two Ag(I) aquo complexes and in two acetonitrile--Cu(I) complexes with dialkylbiphenylphosphane ligands. Arene-Ag(I) complexes with these bulky phosphane ligands show the strongest Ag(I)--arene bonds known.
All that glitters is gold: The total synthesis of the natural enantiomers of englerins A and B has been completed using a gold‐catalyzed stereoselective domino alkyne/alkene/carbonyl cyclization of an enyne with an unprotected alcohol group at a stereogenic allylic position (see scheme; TES=triethylsilyl).
Gold zeigt, was es kann: Die Totalsynthesen der natürlichen Englerin‐Enantiomere A und B gelangen durch goldkatalysierte stereoselektive Alkin‐Alken‐Carbonyl‐Dominocyclisierung eines Enins mit einer ungeschützten Alkoholfunktion an der stereogenen Allylposition (siehe Schema; TES=Triethylsilyl).
Chiral gold(i) phosphite complexes are very reactive precatalysts for the [4+2] cycloaddition of aryl-substituted 1,6-enynes with enantiomeric ratios ranging from 86 : 14 up to 94 : 6.
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