CuI click catalysis with cooperative noninnocent pyridylphosphine ligands

Boer, S.Y. de; Gloaguen, Yann; Lutz, Martin; Vlugt, Jarl Ivar van der

doi:10.1016/j.ica.2011.10.037

Cited by 55 publications

(48 citation statements)

References 91 publications

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“…The synthesis of mononuclear copper(I) acetylide 9 was reported by Gunnoe and co‐workers,27 and its single‐crystal structure affirming the mononuclear nature was reported a few years later by Jones and co‐workers 28. The two copper(I) ions in dinuclear complex 10 engage in σ bonding with acetylide 29. Dinuclear copper(I) acetylide 11 was reported recently by Bertrand and co‐workers,30 in which two copper(I) ions engaged in σ and π bonds, respectively.…”

Section: Copper Complexes With Alkyne or Azidementioning

confidence: 82%

“…Acetate (p K a of acetic acid=4.75) and other carboxylate counterions give fast rates, which can be attributed, in part, to their high basicity and kinetic ability to shuttle protons in organic solvents. The counterion (or ligand)‐catalyzed proton‐transfer step was explicitly described by Diéz‐Gonzaléz and Nolan9 and by van der Vlugt and co‐workers,29 in which the ligand for copper(I) acts as a general base to transfer the alkyne proton to the triazolide.…”

Section: Mechanismmentioning

confidence: 99%

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On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

Zhu

Brassard

Zhang

et al. 2016

The Chemical Record

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The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction regiospecifically produces 1,4-disubstituted-1,2,3-triazole molecules. This heterocycle formation chemistry has high tolerance to reaction conditions and substrate structures. Therefore, it has been practiced not only within, but also far beyond the area of heterocyclic chemistry. Herein, the mechanistic understanding of CuAAC is summarized, with a particular emphasis on the significance of copper/azide interactions. Our analysis concludes that the formation of the azide/copper(I) acetylide complex in the early stage of the reaction dictates the reaction rate. The subsequent triazole ring-formation step is fast and consequently possibly kinetically invisible. Therefore, structures of substrates and copper catalysts, as well as other reaction variables that are conducive to the formation of the copper/alkyne/azide ternary complex predisposed for cycloaddition would result in highly efficient CuAAC reactions. Specifically, terminal alkynes with relatively low pKa values and an inclination to engage in π-backbonding with copper(I), azides with ancillary copper-binding ligands (aka chelating azides), and copper catalysts that resist aggregation, balance redox activity with Lewis acidity, and allow for dinuclear cooperative catalysis are favored in CuAAC reactions. Brief discussions on the mechanistic aspects of internal alkyne-involved CuAAC reactions are also included, based on the relatively limited data that are available at this point.

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Section: Copper Complexes With Alkyne or Azidementioning

confidence: 82%

Section: Mechanismmentioning

confidence: 99%

On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

Zhu

Brassard

Zhang

et al. 2016

The Chemical Record

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“…While this is also the case for the addition of CO 2 and other cumulenes across Py ( R PNP‐H)‐coordinated pincers of type 86 (see Scheme ), the assembly of a new C–C bond may of course also proceed irreversibly. This has been shown by van der Vlugt and co‐workers starting from the κ 2 ‐ P,P ‐ Py ( t BuPNP)‐coordinated copper complex 103 . Upon simple deprotonation, the corresponding T‐shaped copper(I) pincer 104 was produced and isolated in high yields.…”

Section: Pnp Pincers and Their Reactivity Patternsmentioning

confidence: 99%

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

2020

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Aminodiphosphines and their monoanionic amido derivatives are among the most widely used tridentate ligands. A good share of these ligands, in particular the ones that are based on a rigid N‐heterocyclic core, is predisposed to coordinate in a meridional fashion. Negatively charged derivatives of these meridionally coordinating N‐heterocyclic ligands satisfy all the criteria for PNP pincer scaffolds. Herein, these ligands and their coordination chemistry is reviewed from the perspective of coordination chemistry. For our discussion, ligands containing a protonated N‐heterocycle (e.g. pyrrole‐ or carbazole‐based PNP scaffolds) are to be distinguished from their counterparts that do not contain such an NH‐functionality (e.g. pyridine‐ or triazine‐based PNP scaffolds). Different synthetic methodologies for the preparation of PNP pincer complexes are presented and shown to often depend on the presence or absence of the aforementioned NH‐proton. The different reactivity patterns of the resulting complexes are sub‐divided into two categories, namely into metal‐centered reactions and reactions that result in a chemical transformation at the metal and the ligand. The latter represent ligand‐cooperative transformations, which often play a key role in catalysis, and are showcased by discussing selected applications in catalysis. It will become evident in this review that this relatively young research field is still emerging and far from reaching maturity. Finally, a brief overview on ligand/metal combinations that have not been explored to date is provided, to stimulate future research on PNP pincers featuring a central N‐heterocycle.

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“…Initial formation of a phenyl acetylide derivative after reaction of complex 2 with HCCPh (the acetylenic proton is acidic enough to reprotonate the dearomatized ligand) and subsequent addition of benzyl azide led to generation of the triazole product through intramolecular ligand-to-triazole proton transfer. [51] Scheme 10. Generation of unusual dinuclear Cu I complexes with a bridging PNP tBu ligand via sequential dearomatization-reprotonation.…”

Section: Bifunctional Substrate Activationmentioning

confidence: 99%

Cooperative Catalysis with First‐Row Late Transition Metals

2011

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Cooperative catalysis with first-row transition metals holds much promise for future developments regarding sustainable, selective transformations, including e.g. alkenes, dienes and a variety of small molecules such as CO 2 , N 2 and water. This non-exhaustive analysis of the current state-ofthe-art aims to give a comprehensive overview of the various design strategies and applications of first-row transition metal cooperative reactivity and to provide leads for new research initiatives in order to expand this emerging field. The

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CuI click catalysis with cooperative noninnocent pyridylphosphine ligands

Cited by 55 publications

References 91 publications

On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

Cooperative Catalysis with First‐Row Late Transition Metals

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