A new family of cationic, bidentate (P^N)gold(III) fluoride complexes has been prepared and a detailed characterization of the gold‐fluoride bond has been carried out. Our results correlate with the observed reactivity of the fluoro ligand, which undergoes facile exchange with both cyano and acetylene nucleophiles. The resulting (P^N)arylgold(III)C(sp) complexes have enabled the first study of reductive elimination on (P^N)gold(III) systems, which demonstrated that C(sp2)−C(sp) bond formation occurs at higher rates than those reported for analogous phosphine‐based monodentate systems.

DedicatedtoP rofessor Janusz Jurczakont he occasionofh is 75 th birthday.Supporting information for this article is availableonthe WWW under http://dx. Abstract:An enantioselective hydroxyalkylationo f indolesa nd 7-azaindole with trifluoromethyl ketones was found to be effectively promoted under highpressure conditions with al ow loading of Cinchona alkaloids (e.g.,1 -3 mol% of cinchonidine). Chiral tertiary alcohols containingat rifluoromethyl group were obtained at 9kbarw ith good yield and enantio-selectivity up to 89%, whereasu suallym erely traces of productsw ere detected at atmospheric pressure.

The effect of pressure (up to 10 kbar) on the Brønsted acid catalyzed enantioselective hydroxyalkylation of indoles with trifluoromethyl ketones was explored. The reaction was effectively accelerated at 9kbar with av ery low loading of a1 ,1'-bi-2naphthol (BINOL) -derived phosphoric acid (0.05-0.2 mol %o f TRIP) and provided the products with high enantioselectivity (84-98 % ee).Over the last decade, Brønsted acid catalysish as become av ery powerful strategy for the synthesis of enantiomerically enriched molecules. [1] In particular, chiral 3,3'-diaryl-BINOL-derived phosphoric acids (BINOL = 1,1'-bi-2naphthol), successfully introduced by Akiyama [2] and Te rada, [3] are some of the mostu seful and versatile catalysts of this type, as they enable numeroust ypes of asymmetric transformations. [4] However,t heir use in practical applications is limiteda saresult of the need for relatively high loadings (typically ! 5mol %) and the high molecular masses of the catalysts (typically ! 700 gmol À1 ), as well as their availability and cost. [4] Therefore, the development of methods allowing the use of expensive catalysts in very low amountsiso fh igh importance. [5] The aim of our study was to investigate the influence of hydrostatic pressure [6,7] on selected enantioselectiver eactions catalyzed by Brønsted acids, especially 3,3'-diaryl-BINOL-derived phosphoric acids. In recent years, we demonstratedasignificant effect of pressure (8-10 kbar;1kbar = 100 MPa) on difficult organocatalytic 1,4-conjugate addition reactions to congested b,b-disubstituted enones in the presence of chiral amines as catalysts to form products containing quaternary stereogenic centers in good yields with excellent enantioselectivities (up to 99 % ee). [8,9] Also, we found that high pressure remarkably accelerated the reactionb etween indoles andt rifluoroacetophenones in the presence of chiral bases (e.g.,2mol %c inchonidine) with up to 89 % ee. [10] Here, we focusedo ur attention on the enantioselective hydroxyalkylation of indoles [11] with trifluoromethyl ketones [12] in Supporting Information for this article can be foundu nder: https://doi.

A new family of cationic, bidentate (P^N)gold(III) fluoride complexes has been prepared and a detailed characterization of the gold‐fluoride bond has been carried out. Our results correlate with the observed reactivity of the fluoro ligand, which undergoes facile exchange with both cyano and acetylene nucleophiles. The resulting (P^N)arylgold(III)C(sp) complexes have enabled the first study of reductive elimination on (P^N)gold(III) systems, which demonstrated that C(sp2)−C(sp) bond formation occurs at higher rates than those reported for analogous phosphine‐based monodentate systems.