Multicomponent Porphyrin Assemblies as Functional Bidentate Phosphite Ligands for Regioselective Rhodium‐Catalyzed Hydroformylation

Slagt, Vincent F.; Leeuwen, Piet W. N. M. van; Reek, Joost N. H.

doi:10.1002/ange.200352525

Cited by 55 publications

(20 citation statements)

References 69 publications

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“…[22][23][24][25][26][27][28][29] Since this Account is not intended to be a comprehensive review, but rather an illustration of a rapidly developing topic, only a few examples of such studies are discussed below.…”

Section: Encapsulated Transition Metal Reactivitymentioning

confidence: 99%

“…[22][23][24] The pyridyl moieties on the phosphine ligand coordinate to zinc porphyrin complexes, which form well-defined molecular walls. Upon coordination of the phosphine to the metal center, molecular modeling indicates that the reactive metal center is completely encapsulated by the walls of the porphyrin assembly.…”

Section: Encapsulated Transition Metal Reactivitymentioning

confidence: 99%

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Selective Molecular Recognition, C−H Bond Activation, and Catalysis in Nanoscale Reaction Vessels

et al. 2004

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Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M4L6 supramolecular tetrahedron can encapsulate a variety of cationic guests with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated, and the C-H bond activation of aldehydes occurs with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

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Section: Encapsulated Transition Metal Reactivitymentioning

confidence: 99%

Section: Encapsulated Transition Metal Reactivitymentioning

confidence: 99%

Selective Molecular Recognition, C−H Bond Activation, and Catalysis in Nanoscale Reaction Vessels

et al. 2004

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“…In recent years, combinatorial and supramolecular approaches to the development of new ligands for asymmetric catalysis has gained momentum. [1, 2d] The term "supramolecular ligand" encompasses all ligands possessing, besides the atom(s) coordinating to the catalytic metal atom, an additional functionality capable of noncovalent interactions (mainly hydrogen [3] or coordinative bonds [4] ) which can play the following roles: 1) self-assembly of two monodentate ligands to form a so-called supramolecular bidentate ligand; [5] 2) binding the substrate(s) in proximity to the catalytic metal center [2] in analogy to metalloenzymes. [6] Among the different kinds of noncovalent interactions that have been used so far for developing supramolecular ligands, [5] hydrogen bonds are arguably the most practical and efficient [2,3] for several reasons: 1) functional groups capable of hydrogen bonding (e.g., amides, ureas, guanidines) are stable and relatively easy to introduce; 2) hydrogen bonds are created dynamically and reversibly in the reaction medium (where catalysis is to take place), are capable of self-repair when broken, and often coexist with other interactions in a "noninvasive" manner.…”

mentioning

confidence: 99%

PhthalaPhos: Chiral Supramolecular Ligands for Enantioselective Rhodium‐Catalyzed Hydrogenation Reactions

et al. 2010

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Chemists have largely taken inspiration from Nature in the development of new approaches to synthetic challenges. Combinatorial chemistry stems from the concept of evolution, whereby random mutation of a chemical structure gives rise to libraries of compounds, from which an optimal lead can be found with high probability. On the other hand, Nature makes wide use of noncovalent interactions to build its complex supramolecular architectures and to achieve efficient and selective transformations. In recent years, combinatorial and supramolecular approaches to the development of new ligands for asymmetric catalysis has gained momentum. [1, 2d] The term "supramolecular ligand" encompasses all ligands possessing, besides the atom(s) coordinating to the catalytic metal atom, an additional functionality capable of noncovalent interactions (mainly hydrogen [3] or coordinative bonds [4] ) which can play the following roles: 1) self-assembly of two monodentate ligands to form a so-called supramolecular bidentate ligand; [5] 2) binding the substrate(s) in proximity to the catalytic metal center [2] in analogy to metalloenzymes. [6] Among the different kinds of noncovalent interactions that have been used so far for developing supramolecular ligands, [5] hydrogen bonds are arguably the most practical and efficient [2,3] for several reasons: 1) functional groups capable of hydrogen bonding (e.g., amides, ureas, guanidines) are stable and relatively easy to introduce; 2) hydrogen bonds are created dynamically and reversibly in the reaction medium (where catalysis is to take place), are capable of self-repair when broken, and often coexist with other interactions in a "noninvasive" manner.As a result of our continued interest in developing supramolecular ligands, [7] we report herein the design and synthesis of a novel class of chiral monodentate phosphite ligands, named PhthalaPhos, which contain a phthalic acid primary diamide moiety (Scheme 1). The phthalamidic group displays both donor and acceptor hydrogen-bonding properties that, in principle, can give rise to supramolecular interactions both between the ligands and with the reaction substrate. The modular nature of the PhthalaPhos ligands allows their properties to be tuned by simply varying structural elements such as the linker, the binol moiety, and the ancillary amide group (i.e., the amide not connected to the phosphite group), and thus parallel-combinatorial ligand optimization is possible. [1a,c] The PhthalaPhos ligands were easily prepared in four steps as outlined in Scheme 1: phthalic anhydride was treated with a primary amine to give phthalic acid mono amides 1 in 94-98 % yield. [8] Dehydration of the latter in the presence of trifluoroacetic anhydride gave phthalisoimides 2 in high yields, whose reaction with a chosen amino alcohol led to phthalic acid diamides 3.[9] Diamide mono-alcohols 3 were treated with binol-derived chlorophosphites [10] to give Phtha-laPhos ligands 4.Although we synthesized and screened a relatively large library of nineteen members ...

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“…[32] Tauscht man die Rollen von Zink(ii)-Porphyrin-Templat und Stickstoffdonor-Adapter, so ergibt sich ein alternativer Modus zum supramolekularen Aufbau zweizähniger Liganden (Schema 8). [33] Durch Mischen von zwei ¾quivalenten des dreifach Zink(ii) 4). Dies spricht auch hier für die zweizähnige Bindung des Liganden am katalytisch aktiven Metallzentrum.…”

Section: Koordinative Bindungen Als Ligand-ligand-wechselwirkungenunclassified

“…Dies spricht auch hier für die zweizähnige Bindung des Liganden am katalytisch aktiven Metallzentrum. [33] Auf ähnliche Weise wurde ausgehend von Zink(ii)-Porphyrin-funktionalisierten Phosphiten (46-51) und acht Phosphordonorliganden mit zusätzlicher N-Donorfunktion (38-45) eine Bibliothek von 48 Chelatliganden aufgebaut (Schema 9). [34] Tabelle [a]…”

Section: Koordinative Bindungen Als Ligand-ligand-wechselwirkungenunclassified

Supramolekulare Ansätze zur Erzeugung von Bibliotheken zweizähniger Chelatliganden für die homogene Katalyse

Breit

2005

Angewandte Chemie

120

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Die kombinatorische Katalysatorentwicklung und ‐optimierung leidet bislang an der schlechten Zugänglichkeit strukturell diverser Ligandenbibliotheken, vor allem für die Klasse der strukturell komplexeren Chelatliganden. Ein völlig neuer Ansatz umgeht das Problem der schwierigen Ligandensynthese durch die Selbstorganisation von strukturell einfacheren einzähnigen Liganden zu zweizähnigen Liganden durch anziehende nichtkovalente Ligand‐Ligand‐Wechselwirkungen. Bei Verwendung komplementärer Ligand‐Ligand‐Bindungsmotive führt schon einfaches Mischen von jeweils zwei unterschiedlichen einzähnigen Liganden zum Aufbau von Bibliotheken definierter Chelatligand‐Katalysatoren. Dieser Kurzaufsatz fasst die ersten Ansätze und Ergebnisse in diesem vielversprechenden Forschungsgebiet der homogenen Katalyse zusammen.

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Multicomponent Porphyrin Assemblies as Functional Bidentate Phosphite Ligands for Regioselective Rhodium‐Catalyzed Hydroformylation

Cited by 55 publications

References 69 publications

Selective Molecular Recognition, C−H Bond Activation, and Catalysis in Nanoscale Reaction Vessels

Selective Molecular Recognition, C−H Bond Activation, and Catalysis in Nanoscale Reaction Vessels

PhthalaPhos: Chiral Supramolecular Ligands for Enantioselective Rhodium‐Catalyzed Hydrogenation Reactions

Supramolekulare Ansätze zur Erzeugung von Bibliotheken zweizähniger Chelatliganden für die homogene Katalyse

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