Chiral anion strategy in asymmetric organometallic catalysis
This PhD work is devoted to the use of chiral counterion in asymmetric organometallic catalysis. The synthesis of the chiral silver phosphate Ag(S)TRIP was first developed and optimized in order to obtain this high value compound with reproducible yields and high purities. A reactivity study of the original Ru/Au complex bearing an organometallic platform was realized. This complex has shown some interesting reactivity compared to Ph3PAuCl in the particular case of the cycloisomerization of  hydroxyallenynes. Also, the use of the silver phosphate Ag(S)TRIP in association with this bimetallic complex afforded a promising 25% enantiomeric excess in the cycloisomerization of an allenol bearing a gem-diphenyl tether. We reported the first example of chiral counterion catalyzed-carbocyclization of enynes-1,6 thanks to the development of a cationic iridium system in situ generated from the Vaska complex. An original DFT study showed the formation of a substrate-separated ions pair in which the phosphate establishes hydrogen-type bonds with the enyne moiety. We also reported the first examples of cationic rhodium-catalyzed [2+2+2] cycloadditions in which the catalytic species are generated in situ using the chiral counterion Ag(S)TRIP. For the first time, this work proved the original use of a counterion as chiral inductor in the course of cycloadditions processes