Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Abstract

The decrease of reaction temperature can potentially lead to an increase of plasmon-assisted catalytic efficiency.

Evaluation of Dibenzocyclooctyne and Bicyclononyne Click Reaction on Azido‐Functionalized Antifouling Polymer Brushes via Microspotting

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click reactions at the beginning of the 21st century, [1] these reactions are consistently a vital link in the process of biosensing, cell screening, drug delivery, and biofunctionalization. [2][3][4][5][6][7][8] The metal-free click reactions have circumvented the need for toxic catalysts (e.g., Cu I ) and offer a fast reaction rate. [9,10] A successful example is benefitting from the activation by ring strain in the structure of reactants, for example, cycloalkyne or cycloalkane.

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A novel bis-triazole scaffold accessed via two tandem [3 + 2] cycloaddition events including an uncatalyzed, room temperature azide–alkyne click reaction

“…Intramolecular positioning of the click reaction partners may eliminate the need for the metalbased catalyst but the reaction still requires thermal activation [21]. Thus, to our knowledge, the room temperature intramolecular azide-alkyne cycloaddition is unprecedented (plasmonassisted click reaction at low temperature has been recently re-ported [22]). Excited by our initial finding, we tested various azide-containing aromatic aldehydes 3a-i in the reaction with 1 and propargylamine (Scheme 2).…”

Unveiling the role of chemical and electronic structure in plasmon-assisted homolysis of alkoxyamines

“…13,14 All these processes, benefited from plasmonic metal nanostructures, can impel plasmonic chemistry. However, recent studies 13,14,15 including ours 8,10 cast a doubt on mechanisms (1) and (2) but provide more evidence about intramolecular excitation process (3) in some cases.…”

“…Originally, the plasmonic approach was successfully applied toward enhancing catalysis of inorganic reactions such as CO/CO2 reduction or water splitting 3,4 , but organic reactions could not shot out for a long 5 . The utilization of plasmon catalysis opens a huge potential for improved selectivity 6,7 , enhanced reaction rates 8,9 , and milder reaction conditions 10 . Up to now, the range of plasmon-assisted organic reactions was reported, such as oxidation of alcohols, amines, and unsaturated compounds; reductive transformations; C−C and C−N bond formation; and polymerization 5 .…”

“…We have demonstrated that alkoxyamines (AAs) R1R2NOR3 are molecules that homolyze into nitroxides (R1R2NO•) and reactive alkyl radicals (R3•), can be monitored by precise EPR measurements, under plasmon excitation on the gold surface. 10,18 Thus, there is a genuine need, from both fundamental and applied viewpoints, to elucidate the role of the nature/structure of molecules and their electronic structure to the plasmonic chemistry. Filling this gap promises to unlock an unprecedented control over kinetic and thermodynamic parameters of organic reactions and to carefully develop the plasmonic catalysts for organic transformations.…”