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Uranyl.triflate as selective catalyst in the hydrosilylation of aldehydes

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Abstract

The chemistry of uranium has atlracted considerable attention in industrial and environmental fields and fundamental researches have revealed unique chemical features of this element. For years, transformation of oxygenated compounds with actinide catalysts was not considered due to the strength of the actinide-oxygen bond that should preclude efficient catalytic turnover. However, this idea vanished in 2008 when the group of Eisen unveiled the ability of actinide(IV) complexes (U and Th) to promote the catalytic dimerization of aldehydes. 1 A few reports now describe activation of oxygen substrates with U4+, Th 4 + and [U0 2 ]2+ complexes. 2 While the reduction of oxygenated substrates, involving the cleavage of CO and/or C=O bonds, is of fundamental importance, the utilization of actinide catalysts in this area is extremely rare. In particular, hydrosilanes (R3SiH) have never been combined with the 5f elements for the reduction of carbonyl groups although the slight polarization of the Si-H bond displays advantages for the development of selective reduction processes in organic ,chemistry, the valorization of biomass, 3 and the recycling of plastics. Here, we report the first use of an actinide complex to carry out catalytic hydrosilylation of C=O bonds. 5 The uranyl cation [U02]2+,which is the most oxidized uranium fragment ubiquitous in the environ ment and in the nuclear industry, proved, as the uranyl triflate species, an efficient catalyst in the reductive hydrosilylation of aldehydes into symmetric ethers and silylated alcohols depending on the nature of the hydrosilane (Scheme 1). The reactions also show that, although the uranyl ion contains oxidi~ing U=O bonds, reductionûfthe C=O group and CO bond cleavage are possible without loss of integrity of the uranyl moiety.
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Dates and versions

cea-02329560 , version 1 (23-10-2019)

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  • HAL Id : cea-02329560 , version 1

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Jean-Claude Berthet, Louis Monsigny, Pierre Thuéry, Thibault Cantat. Uranyl.triflate as selective catalyst in the hydrosilylation of aldehydes. GECOM-CONCOORD 2019, May 2019, Erquy, France. ⟨cea-02329560⟩
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