Phosphine–phosphite ligands in the palladium-catalyzed asymmetric allylic alkylation: Electronic and steric effects

Farkas, Gergely; Császár, Zsófia; Balogh, Szabolcs; Szöllősy, Áron; Gouygou, Maryse; Bakos, József

doi:10.1016/j.catcom.2013.03.005

Cited by 14 publications

(3 citation statements)

References 33 publications

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“…Several types of heterodonor P,P′-ligands were evaluated in Pd-catalyzed allylations, most of them heterodonor phosphine-containing ligands (e.g., phosphine-phosphoramidite, phosphine-diaminophosphine oxide and phosphine-phosphite), − although phosphite-phosphoramidite ligands generally performed better in terms of enantioselectivitiy and substrate scope. − Of the latter group, we highlight two families, ligands of type L53 derived from 1,2-amino alcohols and L54 with a furanoside backbone . All of them share the advantage of a modular structure and short syntheses from readily available starting materials and are also air stable.…”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

219

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

219

View full text Add to dashboard Cite

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“…For homogeneous (transition) metal catalysts it is more facile to obtain molecular-scale information of the active species, which in turn aids in unraveling the reaction mechanism of specific reactions (Cornils and Herrmann, 2002; Ferreira et al, 2004). It is now well-recognized that the use of electronically and/or sterically tuned ligands can lead to enhanced catalytic performance of the corresponding metal complexes (Trost et al, 1992; van Leeuwen, 2004; Praneeth et al, 2012; Farkas et al, 2013; Karroumi et al, 2015). Nonetheless, the rational design of tailor-made catalysts for specific transformations is still in its infancy, and systematic screening of catalysts is the main practice to “discover” new catalysts.…”

Section: Introductionmentioning

confidence: 99%

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

et al. 2018

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This review focuses on the effects that confinement of molecular and heterogeneous catalysts with well-defined structure has on the selectivity and activity of these systems. A general introduction about catalysis and how the working principles of enzymes can be used as a source of inspiration for the preparation of catalysts with enhanced performance is provided. Subsequently, relevant studies demonstrate the importance of second coordination sphere effects in a broad sense (in homogeneous and heterogeneous catalysis). Firstly, we discuss examples involving zeolites, MOFs and COFs as heterogeneous catalysts with well-defined structures where confinement influences catalytic performance. Then, specific cases of homogeneous catalysts where non-covalent interactions determine the selectivity and activity are treated in detail. This includes examples based on cyclodextrins, calix[n]arenes, cucurbit[n]urils, and self-assembled container molecules. Throughout the review, the impact of confined spaces is emphasized and put into context, in order to get a better understanding of the effects of confinement on catalyst performance. In addition, this analysis intends to showcase the similarities between homogeneous and heterogeneous catalysts, which may aid the development of novel strategies.

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“…This parameter generally increases as the σ‐donor strength of the corresponding P(III) fragment decreases 22. Thus, values for phosphine–selenides roughly lie in the range between 700 and 750 Hz, whereas for selenophosphates coupling constants between 1020 and 1060 Hz are typically observed 23,24. Notably, the cyclic nature of phosphite fragments present in P‐OP ligands also reduces the σ‐donor character of the corresponding phosphites because the values of their selenophosphates are about 30–40 Hz higher than those of acyclic phosphites 22a…”

Section: Features Of P‐op Ligandsmentioning

confidence: 99%

Features and Application in Asymmetric Catalysis of Chiral Phosphine–Phosphite Ligands

Pizzano

2016

The Chemical Record

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Chiral phosphine-phosphites are a class of ligands for asymmetric catalysis characterized by two coordinating functionalities with different electronic properties. These ligands also possess a highly modular structure and, due to versatile synthetic processes, they can be tuned precisely in the catalyst optimization process. Research regarding the application of these ligands in several enantioselective catalytic processes has provided outstanding results in a good number of them. These processes include not only Rh catalyzed reactions, such as olefin hydrogenation and hydroformylation, but also other reactions, such as hydrogenation of olefins and imines by Ru complexes, of imines and N-heterocycles by Ir derivatives, allyl alkylation or conjugate addition by Cu catalysts, or hydrocyanation of olefins by Ni ones. Overall, the use of these ligands has led to the preparation of a wide variety of chiral building blocks with high enantiomeric excess. Therefore, phosphine-phosphites have become in an important class of ligands in asymmetric catalysis.

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Phosphine–phosphite ligands in the palladium-catalyzed asymmetric allylic alkylation: Electronic and steric effects

Cited by 14 publications

References 33 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Confinement Effects in Catalysis Using Well-Defined Materials and Cages

Features and Application in Asymmetric Catalysis of Chiral Phosphine–Phosphite Ligands

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