A novel yttrium-based metal–organic framework for the efficient solvent-free catalytic synthesis of cyanohydrin silyl ethers

Abstract

A novel MOF has been synthesized, characterized, and applied in the cyanosilylation of aldehydes and ketones being the first example of an yttrium MOF able to catalyze this reaction.

A Mixed Heterobimetallic Y/Eu-MOF for the Cyanosilylation and Hydroboration of Carbonyls

“…The obtained values for cyanosilylation reaction were 100% of AE, 1.127 for MI, 95.7% for RME, and 96.8% for CE. These results are comparable to those described previously for related lanthanide-based MOFs [15,16,19,20]. In the case of the hydroboration reaction, these values decreased considerably, down to 49.1%, 2.406, 46.8%, and 52.1% for AE, MI, RME, and CE, respectively, due to the final hydrolysis and consequent loss of atoms in the final product (Table S9).…”

“…The catalytic activity of Y/Eu-MOF (0.5 mol%) was initially evaluated in the cyanosilylation reaction of carbonyl compounds (Y/Eu-MOF) using TMSCN as the nucleophile, solvent free reaction conditions, room temperature, and N 2 atmosphere. These conditions have been already reported in our previous works, with monometallic Y or Eu MOF synthetized with the same ligand H 2 L (3-amino-4-hydroxybenzoic acid) [15], obtaining only 8% conversion after 14 h when the blank reaction was tested.…”

“…Nonetheless, within this frame of reference, the number of reported Ln-MOF acting as a heterogeneous catalyst in the cyanosilylation reaction results were relatively scarce 2 of 10 (Table S10 summarizes the reported examples exhibiting activity, so far) [5,[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. Moreover, to the best of our knowledge, lanthanide-based heterobimetallic MOFs have never been applied.…”

“…The synthesis of alcohols through this route has been explored via MOF systems based on Ti, Fe, Co, and Mg [25][26][27][28][29][30]; however, there are no precedents with these supramolecular entities built on lanthanides precursors. Therefore, in this work, the first example of yttrium and europiumbased mixed MOF, with the formula {[Y 3.5 Eu 1.5 L 6 (OH) 3 (H 2 O) 3 ]•12DMF} n , is presented, taking the strong background of our group in the examination of these supramolecular systems in catalysis [15,16].…”

“…The heterobimetallic Y/Eu-MOF presented herein was designed when looking for a synergy and enhanced catalytic activity, with respect to their isostructural pristine counterparts, which were able to exhibit activity for seven cycles, with very low catalytic loading of 0.5 mol%, no catalyst leaking, TOF values of 106 h −1 and 1031 h −1 , and preferred suitability towards aldehydic and ketonic substrates for Y-MOF [15] and Eu-MOF, respectively.…”