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Catalytic hydroboration and cyanosilylation of a wide range of aldehydes and ketones, with pinacolborane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) and trimethylsilyl cyanide, respectively, in the presence of titanium(IV) complexes [κ2-{(C5H4N)CH2N-P(=Se)Ph2}Ti(NMe2)3] (1) and [{κ2-(C6H4F)NP(=Se)Ph2}Ti(NMe2)3] (2) are reported. The catalytic hydroboration and cyanosilylation processes are high-yielding and general, and result in efficient conversion of carbonyl compounds into the corresponding products under mild conditions. Titanium catalyst 1 exhibits high tolerance toward several functional groups. First-order kinetics with respect to the catalyst and each of the substrates were observed for the titanium-catalyzed hydroboration of carbonyl compounds. First-principles calculations were performed to explore the catalytic hydroboration reaction mechanism. In addition, a combination of both reactions and sequential cyanosilylation/hydroboration is reported. TiIV complexes 1 and 2 were prepared by aminolysis of [Ti(NMe2)4] with protic ligands [(C5H4N)CH2NHP(=Se)Ph2] (L1H) and [(C6H4F)NHP(=Se)Ph2] (L2H), respectively. The third titanium complex [κ4-{Ph2P(=Se)NCH(C5H4N)CH(C5H4N)P(=Se)Ph2}-Ti(NMe2)2] (3) was obtained from the reaction between [Ti(NMe2)4] and ligand L1H in a 1:2 molar ratio at room temperature. The molecular structures of complexes 1 and 3 in the solid state are reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Journal | Data powered by TypesetEuropean Journal of Organic Chemistry |
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Publisher | Data powered by TypesetWiley-VCH Verlag |
ISSN | 1434193X |