1394246-13-9Relevant academic research and scientific papers
Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex
Sung, Simon,Boon, Jie Kang,Lee, Johnathan J. C.,Rajabi, Nasir A.,Macgregor, Stuart A.,Kr?mer, Tobias,Young, Rowan D.
, p. 1609 - 1617 (2017)
We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an α-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the α-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(2-carbonyl) complex (4). C-H activation in 2 at the proligand's central methine position, rather than O-H activation of the hydroxy motif, followed by loss of dihydrogen also generates the α-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports α-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be noninnocent coligands in reported hydrogenation catalyst systems in which they are utilized.
