Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts

2017 ◽  
Vol 50 (9) ◽  
pp. 2147-2158 ◽  
Author(s):  
Juliet M. Alderson ◽  
Joshua R. Corbin ◽  
Jennifer M. Schomaker
Keyword(s):  
Rational Design ◽  
Transfer Reactions ◽  
Nitrene Transfer ◽  
Site Selective

Catalyst-Controlled Site-Selective N-H and C3-Arylation of Carba-zole via Carbene Transfer Reactions

2021 ◽  
Author(s):  
Sourav Sekhar Bera ◽  
Srishti Ballabh Bahukhandi ◽  
Claire Empel ◽  
Rene M Koenigs
Keyword(s):  
Transfer Reactions ◽  
Palladium Acetate ◽  
Direct Arylation ◽  
Carbene Transfer ◽  
A Site ◽  
Site Selective

A site-selective direct arylation reaction of carbazole and other N-heterocycles with diazo-naphthalen-2(1H)-ones has been developed. While Au(I)-NHC catalysts lead to selective C3-arylation, palladium acetate allows for selective N-H arylation, displaying...

scholarly journals A combined experimental and theoretical study on the reactivity of nitrenes and nitrene radical anions

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Yujing Guo ◽  
Chao Pei ◽  
Rene M. Koenigs
Keyword(s):  
Radical Anion ◽  
Room Temperature ◽  
Theoretical Study ◽  
Transition Metal Catalysts ◽  
Transfer Reactions ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Nitrene Transfer ◽  
Triplet Nitrene ◽  
Nitrogen Bonds

AbstractNitrene transfer reactions represent one of the key reactions to rapidly construct new carbon-nitrogen bonds and typically require transition metal catalysts to control the reactivity of the pivotal nitrene intermediate. Herein, we report on the application of iminoiodinanes in amination reactions under visible light photochemical conditions. While a triplet nitrene can be accessed under catalyst-free conditions, the use of a suitable photosensitizer allows the access of a nitrene radical anion. Computational and mechanistic studies rationalize the access and reactivity of triplet nitrene and nitrene radical anion and allow the direct comparison of both amination reagents. We conclude with applications of both reagents in organic synthesis and showcase their reactivity in the reaction with olefins, which underline their markedly distinct reactivity. Both reagents can be accessed under mild reaction conditions at room temperature without the necessity to exclude moisture or air, which renders these metal-free, photochemical amination reactions highly practical.

scholarly journals Ternary MOF-on-MOF heterostructures with controllable architectural and compositional complexity via multiple selective assembly

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Chao Liu ◽  
Qiang Sun ◽  
Lina Lin ◽  
Jing Wang ◽  
Chaoqi Zhang ◽  
...  
Keyword(s):  
Rational Design ◽  
Materials Science ◽  
Metal Organic Framework ◽  
Building Blocks ◽  
Selective Assembly ◽  
Assembly Strategy ◽  
Metal Organic ◽  
Site Selective ◽  
Organic Framework ◽  
The Way

Abstract Assembly of different metal-organic framework (MOF) building blocks into hybrid MOF-on-MOF heterostructures is promising in chemistry and materials science, however the development of ternary MOF-on-MOF heterostructures with controllable architectural and compositional complexity is challenging. Here we report the synthesis of three types of ternary MOF-on-MOF heterostructures via a multiple selective assembly strategy. This strategy relies on the choice of one host MOF with more than one facet that can arrange the growth of a guest MOF, where the arrangement is site-selective without homogenous growth of guest MOF or homogenous coating of guest on host MOF. The growth of guest MOF on a selected site of host MOF in each step provides the opportunity to further vary the combinations of arrangements in multiple steps, leading to ternary MOF-on-MOF heterostructures with tunable complexity. The developed strategy paves the way towards the rational design of intricate and unprecedented MOF-based superstructures for various applications.

scholarly journals Disentangling the size-dependent geometric and electronic effects of palladium nanocatalysts beyond selectivity

2019 ◽  
Vol 5 (1) ◽  
pp. eaat6413 ◽  
Author(s):  
Hengwei Wang ◽  
Xiang-Kui Gu ◽  
Xusheng Zheng ◽  
Haibin Pan ◽  
Junfa Zhu ◽  
...  
Keyword(s):  
Metal Nanoparticles ◽  
Rational Design ◽  
Aerobic Oxidation ◽  
Atomic Layer ◽  
Electronic Effects ◽  
Coordination Sites ◽  
Layer Deposition ◽  
Palladium Nanocatalysts ◽  
The Right ◽  
Site Selective

The prominent size effect of metal nanoparticles shapes decisively nanocatalysis, but entanglement of the corresponding geometric and electronic effects prevents exploiting their distinct functionalities. In this work, we demonstrate that in palladium (Pd)–catalyzed aerobic oxidation of benzyl alcohol, the geometric and electronic effects interplay and compete so intensively that both activity and selectivity showed in volcano trends on the Pd particle size unprecedentedly. By developing a strategy of site-selective blocking via atomic layer deposition along with first principles calculations, we disentangle these two effects and unveil that the geometric effect dominates the right side of the volcano with larger-size Pd particles, whereas the electronic effect directs the left of the volcano with smaller-size Pd particles substantially. Selective blocking of the low-coordination sites prevents formation of the undesired by-product beyond the volcano relationship, achieving a remarkable benzaldehyde selectivity and activity at the same time for 4-nm Pd. Disentangling the geometric and electronic effects of metal nanoparticles opens a new dimension for rational design of catalysts.

A Diiron(III,IV) Imido Species Very Active in Nitrene-Transfer Reactions

2014 ◽  
Vol 53 (6) ◽  
pp. 1580-1584 ◽  
Author(s):  
Eric Gouré ◽  
Frédéric Avenier ◽  
Patrick Dubourdeaux ◽  
Olivier Sénèque ◽  
Florian Albrieux ◽  
...  
Keyword(s):  
Transfer Reactions ◽  
Nitrene Transfer

scholarly journals Nitrene Transfer Reactions Catalyzed by Gold Complexes.

ChemInform ◽  
2006 ◽  
Vol 37 (48) ◽  
Author(s):  
Zigang Li ◽  
Xiangyu Ding ◽  
Chuan He
Keyword(s):  
Transfer Reactions ◽  
Gold Complexes ◽  
Nitrene Transfer
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