TitleSynthesis of new phosphorus ligands for regioselective hydroformylation
NameChie, Yu-Ming (author), Zhang, Xumu (chair), Seidel, Daniel (internal member), Jimenez, Leslie (internal member), Rutgers University, Graduate School - New Brunswick,
DescriptionTetraphosphorous ligands with enhanced chelating ability through multiple chelating modes and increased local phosphorus concentration can provide great regioselectivity in Rh/Ligand hydroformylation system. Here we report the synthesis of a series of pyrrole-based tetraphosphorus ligands were synthesized with introducing different functional groups into 3, 3', 5, 5'-positions of the biphenyl, and their applications to the hydroformylation of internal olefins, 1, 5-hexadiene, styrene and its derivatives, and alkyl acrylates.
Internal olefins are cheaper and more readily available feedstock than terminal olefins, the development of highly selective and active isomerization-hydroformylation catalysts for internal olefins is of great importance from economic and energy points of view. In particular, the alkyl-substituted tetraphosphorous ligands gave the best results (for 2-octene, n: i up to 207, for 2-hexene, n: i up to 362).
Double hydroformylation of 1, n-diolefins is a convenient method to produce dialdehydes. The hydroformylation of 1, 5- hexadiene can be achieved with essentially high regioselectivity (linear selectivity is up to 98%).
Styrene and its derivatives prefer the branched aldehydes under the hydro-formylation conditions. However, the linear aldehydes can also be widely used for the production of detergents and plasticizers and important intermediates. Our studies on the hydroformylation of styrene and its derivatives achieved unprecedented high linear selectivity (l/b up to 22 for styrene).
Hydroformylation of alkyl acrylate produces 1, 3- and1, 4-bifunctional compounds, which can be further converted into synthetically useful intermediates. Alkyl acrylates have been hydroformylated to the linear aldehydes with high regioselectivity (linear/branch > 99/1) and extraordinarily high average turnover frequencies (up to 5400 h 1) by using a rhodium complex with a tetraphosphorus ligand. The result is in sharp contrast to the most of other processes that favor production of the branched aldehyde (typically > 95% branched for most Rh-catalyzed reaction systems).
NoteIncludes bibliographical references
Noteby Yu-Ming Chie
CollectionGraduate School - New Brunswick Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.