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Rhodium‐Catalyzed Hydrogenation of Alkenes by Rhodium/Tris(fluoroalkoxy)phosphane Complexes in Fluorous Biphasic System
Author(s) -
Sinou Denis,
Maillard David,
Aghmiz Ali,
Masdeu iBultó Anna M.
Publication year - 2003
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200202122
Subject(s) - rhodium , chemistry , catalysis , medicinal chemistry , cinnamaldehyde , acceptor , organic chemistry , physics , condensed matter physics
The reaction of [Ir(μ‐Cl)(COD)] 2 with various fluorous derivatives of triphenylphosphane containing a para ‐, meta ‐, or ortho ‐(1 H ,1 H ‐perfluoroalkoxy)‐substituted fluorous phosphane P(C 6 H 4 ‐ORf) 3 (Rf=CH 2 C 7 F 15 , CH 2 CH 2 CH 2 C 8 F 17 ) and CO (1 atm) gives the corresponding trans‐ [Ir(μ‐Cl)(CO){P(C 6 H 4 ORf) 3 } 2 ]. The IR ν CO values of these complexes give some information on the donor/acceptor properties of the phosphanes. These fluorous derivatives of triphenylphosphane, as well as a phosphane bearing two (1 H ,1 H ‐perfluoroalkyloxy) chains at the 3,5‐positions, were used in association with [Rh(μ‐Cl)(COD)] 2 or [Rh(COD) 2 ]PF 6 in the reduction of methyl cinnamate, 2‐cyclohexen‐1‐one, cinnamaldehyde, and methyl α‐acetamidocinnamate in a two‐phase system D‐100/ethanol under 1 bar hydrogen at room temperature. Some differences in catalytic activity were observed in the reduction of methyl cinnamate, the most active catalyst being the rhodium complex containing the phosphane with the p ‐fluorous ponytail. Recycling of the fluorous catalyst was possible, particularly using the p ‐substituted phosphane, where no significant loss of catalyst or activity was observed, and generally with very low leaching of rhodium or phosphane in the organic phase.