Screening of a Supramolecular Catalyst Library in the Search for Selective Catalysts for the Asymmetric Hydrogenation of a Difficult Enamide Substrate

Jiang, Xiao-Bin; Lefort, Laurent; Goudriaan, P. Elsbeth; Vries, André H.M. de; Leeuwen, Piet W. N. M. van; Vries, Johannes G. de; Reek, Joost N. H.

doi:10.1002/anie.200503663

Cited by 190 publications

(56 citation statements)

References 58 publications

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“…For example, means to predict the selectivity provided by transition metal catalyst are lacking, and therefore high throughput screening of libraries of catalysts is still the most powerful method to find catalyst systems with desired selectivities. Indeed, we and others have introduced supramolecular ways to make transition metal catalysts and used the building block approach to create large libraries of related catalysts, some of which show unrivaled selectivities (5)(6)(7)(8)(9).…”

mentioning

confidence: 99%

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Kluwer

Kapre²,

Hartl³

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

212

137

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The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a supramolecular biomimetic approach to form a catalyst that produces molecular hydrogen using light as the energy source. It is composed of an assembly of chromophores to a bis(thiolate)-bridged diiron ([2Fe2S]) based hydrogenase catalyst. The supramolecular building block approach introduced in this article enabled the easy formation of a series of complexes, which are all thoroughly characterized, revealing that the photoactivity of the catalyst assembly strongly depends on its nature. The active species, formed from different complexes, appears to be the [Fe 2(-pdt)(CO)4{PPh2(4-py)}2] (3) with 2 different types of porphyrins (5a and 5b) coordinated to it. The modular supramolecular approach was important in this study as with a limited number of building blocks several different complexes were generated.photocatalysis ͉ self-assembly ͉ supramolecular chemistry ͉ metalloporphyrin chromophore ͉ Stern-Volmer plot S upramolecular chemistry, defined by Nobel Prize Laureate Jean-Marie Lehn as the ''chemistry beyond the molecule,'' has changed the way we look at molecules (1). Besides exploring reactivity of molecules, interaction between molecules has become of dominant importance as it provides new means of controlling properties of chemical systems. Supramolecular chemistry has rapidly evolved into a mature field, and the implementation of supramolecular strategies has resulted in breakthroughs in several disciplines (2-4). The reversible character of noncovalent chemistry gives rise to concepts such as adaptation and self-correction, creating fundamentally different system properties compared with traditional covalent strategies. The modular character associated with the building block approach in supramolecular chemistry provides an easy strategy to generate large libraries of analogous structures of nanosize dimension. Such libraries are of interest in research areas where accurate prediction of particular properties of chemical systems is inadequate or impossible. For example, means to predict the selectivity provided by transition metal catalyst are lacking, and therefore high throughput screening of libraries of catalysts is still the most powerful method to find catalyst systems with desired selectivities. Indeed, we and others have introduced supramolecular ways to make transition metal catalysts and used the building block approach to create large libraries of related catalysts, some of which show unrivaled selectivities (5-9).Stimulated by these exciting results, we were wondering whether supramolecular strategies could also provide solutions to other challenges in catalysis. One of the greatest challenges our society is currently facing is the large-scale production of clean energy (10). Molecular hydrogen is e...

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mentioning

confidence: 99%

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Kluwer

Kapre²,

Hartl³

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

212

137

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“…Most interestingly, substrate 1e, which should apparently be more encumbered than the latter enamides, is significantly more reactive. Thus, catalysts bearing ligands 4a, 4m and 4l gave full conversions for this substrate (entries [6][7][8]. Among the catalysts investigated, that based on 4l produced again the best enantioselectivity (93 % ee).…”

Section: Rc(o)mentioning

confidence: 99%

“…8 Following an approach based on the generation of chelating ligands from monodentate assembling ones, these researchers have achieved a catalyst which provides an outstanding 94 % ee in the hydrogenation of N- (3,4-dihydronaphthalen-2-yl) acetamide.…”

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confidence: 99%

Rhodium Phosphine–Phosphite Catalysts in the Hydrogenation of Challenging N-(3,4-dihydronaphthalen-2-yl) Amide Derivatives

et al. 2013

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ABSTRACT. The enantioselective catalytic hydrogenation of N- (3,4-dihydronaphthalen-2-yl) amides (1) with rhodium catalysts bearing phosphine-phosphite ligands 4 has been studied. A wide catalyst screening, facilitated by the modular structure of 4, has found a highly enantioselective catalyst for this reaction. This catalyst gives a 93 % ee in the hydrogenation of 1a and also produces high enantioselectivities, ranging from 83 to 93 % ee, in the hydrogenation of several -OMe and -Br substituted substrates. On the contrary, structurally related enol esters 2 are very reluctant to the hydrogenation. A coordination study of representative enamide 1d has shown an unusual η 6 -arene coordination mode, over the typical O,C,C chelating mode for enamides, as the preferred one for this substrate in a Rh(I) complex. Deuteration reactions of 1c and 1d indicate a clean syn addition of deuterium to the double bond without isotopic effect on enantioselectivity.

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“…[34][35][36][37][38] In particular, phosphites and phosphoramidites with BINOL or TADDOL backbone and metalloporphyrin fragment have proven to be highly advantageous building blocks in creating large libraries of supramolecular ligands. [34][35][36][37][38][39][40][41][42][43] However, according to our best knowledge, there is only one brief mention of chiral phosphite bearing porphyrin core without a metal ion. [40] In this paper, we report on the preparation of a small series of phosphite and diamidophosphite ligands containing metal-free porphyrin framework, that we had subsequently explored in Pd-catalyzed asymmetric allylation reactions.…”

Section: Introductionmentioning

confidence: 99%

“…[34][35][36][37][38][39][40][41][42][43] However, according to our best knowledge, there is only one brief mention of chiral phosphite bearing porphyrin core without a metal ion. [40] In this paper, we report on the preparation of a small series of phosphite and diamidophosphite ligands containing metal-free porphyrin framework, that we had subsequently explored in Pd-catalyzed asymmetric allylation reactions.…”

Section: Introductionmentioning

confidence: 99%

Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

Konstantin¹,

Sergey²,

Marina³

et al. 2015

MHC

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Screening of a Supramolecular Catalyst Library in the Search for Selective Catalysts for the Asymmetric Hydrogenation of a Difficult Enamide Substrate

Cited by 190 publications

References 58 publications

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Rhodium Phosphine–Phosphite Catalysts in the Hydrogenation of Challenging N-(3,4-dihydronaphthalen-2-yl) Amide Derivatives

Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

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