TY - JOUR
T1 - Triruthenium dodecacarbonyl/triphenylphosphine catalyzed dehydrogenation of primary and secondary alcohols
AU - Meijer, R.H.
AU - Ligthart, G.B.W.L.
AU - Meuldijk, J.
AU - Vekemans, J.A.J.M.
AU - Hulshof, L.A.
AU - Mills, A.M.
AU - Kooijman, H.
AU - Spek, A.L.
PY - 2004
Y1 - 2004
N2 - Dehydrogenation of alcs. into aldehydes and ketones by Ru3(CO)12/PPh3 based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidn. Several catalytic systems have been screened in the Oppenauer-like oxidn. of alcs. A systematic study of various combinations of Ru3(CO)12, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcs. to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth redn. Electron rich and deficient analogs of tolane have been synthesized and, based on competition expts. between these H-acceptors, a tentative catalytic cycle for the Ru3(CO)12/PPh3-catalyzed dehydrogenations has been proposed. The crystal and mol. structures of a ruthenium-triphenylphosphine-tolane adduct [i.e., dicarbonyl[(2,3,4,5-h)-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one](triphenylphosphine)ruthenium] were reported. [on SciFinder (R)]
AB - Dehydrogenation of alcs. into aldehydes and ketones by Ru3(CO)12/PPh3 based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidn. Several catalytic systems have been screened in the Oppenauer-like oxidn. of alcs. A systematic study of various combinations of Ru3(CO)12, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcs. to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth redn. Electron rich and deficient analogs of tolane have been synthesized and, based on competition expts. between these H-acceptors, a tentative catalytic cycle for the Ru3(CO)12/PPh3-catalyzed dehydrogenations has been proposed. The crystal and mol. structures of a ruthenium-triphenylphosphine-tolane adduct [i.e., dicarbonyl[(2,3,4,5-h)-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one](triphenylphosphine)ruthenium] were reported. [on SciFinder (R)]
U2 - 10.1016/j.tet.2003.11.082
DO - 10.1016/j.tet.2003.11.082
M3 - Article
SN - 0040-4020
VL - 60
SP - 1065
EP - 1072
JO - Tetrahedron
JF - Tetrahedron
IS - 5
ER -