Rhodium-catalyzed triazole-directed C–H bond functionalization of arenes with diazo compounds

2018 ◽  
Vol 16 (43) ◽  
pp. 8191-8195 ◽  
Author(s):  
Huanhong Wang ◽  
Xiaofei Yi ◽  
Yanli Cui ◽  
Wanzhi Chen
Keyword(s):  
Diazo Compounds ◽  
Bond Functionalization ◽  
Alkylation Reactions

Rhodium(iii)-catalyzed alkylation reactions of arenes through triazole directed C–H activation that lead to a number of dialkylated and monoalkylated triazoles are described.

scholarly journals Recent Advances in Palladium-Catalyzed Bridging C–H Activation by Using Alkenes, Alkynes or Diazo Compounds as Bridging Reagents

Synthesis ◽  
2020 ◽  
Vol 53 (02) ◽  
pp. 238-254
Author(s):  
Fulin Zhang ◽  
Luoting Xin ◽  
Saihu Liao ◽  
Xueliang Huang ◽  
Yinghua Yu
Keyword(s):  
Bond Distance ◽  
Short Review ◽  
Diazo Compounds ◽  
Bond Functionalization ◽  
Migratory Insertion ◽  
Intramolecular Reactions ◽  
Palladium Catalyzed ◽  
Direct Functionalization ◽  
Intermolecular Reactions ◽  
Metal Catalyzed

AbstractTransition-metal-catalyzed direct inert C–H bond functionalization has attracted much attention over the past decades. However, because of the high strain energy of the suspected palladacycle generated via C–H bond palladation, direct functionalization of a C–H bond less than a three-bond distance from a catalyst center is highly challenging. In this short review, we summarize the advances on palladium-catalyzed bridging C–H activation, in which an inert proximal C–H bond palladation is promoted by the elementary step of migratory insertion of an alkene, an alkyne or a metal carbene intermediate.1 Introduction2 Palladium-Catalyzed Alkene Bridging C–H Activation2.1 Intramolecular Reactions2.2 Intermolecular Reactions3 Palladium-Catalyzed Alkyne Bridging C–H Activation3.1 Intermolecular Reactions3.2 Intramolecular Reactions4 Palladium-Catalyzed Carbene Bridging C–H Activation5 Conclusion and Outlook

scholarly journals Mechanism of Side Reactions in Alkane CH Bond Functionalization by Diazo Compounds Catalyzed by Ag and Cu Homoscorpionate Complexes-A DFT Study

ChemCatChem ◽  
2011 ◽  
Vol 3 (10) ◽  
pp. 1646-1652 ◽  
Author(s):  
Ataualpa A. C. Braga ◽  
Ana Caballero ◽  
Juan Urbano ◽  
M. Mar Diaz-Requejo ◽  
Pedro J. Pérez ◽  
...  
Keyword(s):  
Dft Study ◽  
Diazo Compounds ◽  
Side Reactions ◽  
Bond Functionalization

Iron-catalysed chemo- and ortho-selective C-H bond functionalization of phenols with -aryl--diazoacetates

2021 ◽  
Author(s):  
Zhunzhun Yu ◽  
Guanghui Li ◽  
Junliang Zhang ◽  
Lu Liu
Keyword(s):  
Catalytic Activity ◽  
Diazo Compounds ◽  
Iron Porphyrin ◽  
Bond Functionalization

Herein we present a novel iron-catalyzed chemo- and regio-selective ortho C-H bond functionalization of phenols and naphthols with diazo compounds. In this transformation, iron porphyrin exhibits specificly catalytic activity, which...

Selective Synthesis of 2- and 7-Substituted Indole Derivatives via Chelation-Assisted Metallocarbenoid C–H Bond Functionalization

Synthesis ◽  
2017 ◽  
Vol 50 (02) ◽  
pp. 227-240 ◽  
Author(s):  
Sergey Osipov ◽  
Daria Vorobyeva
Keyword(s):  
Short Review ◽  
Diazo Compounds ◽  
Indole Derivatives ◽  
Metal Catalysis ◽  
Bond Functionalization ◽  
Drug Candidates ◽  
Directing Group ◽  
Metal Catalyzed ◽  
Related Compounds ◽  
Made In

Functionally substituted indole derivatives are important intermediates for the synthesis of new potential drug candidates exhibiting strong bioactivities. Over the past few years, significant progress has been made in the direct C–H functionalization of the indole ring through the usage of metal-catalyzed intermolecular cross-coupling with diazo compounds. Directing group strategy provides a unique possibility for selective insertion of carbenes catalytically generated from diazo compounds into challenging indole C2–H and C7–H bonds. This short review summarizes recent advances in carbenoid functionalization of indole derivatives under chelation-controlled metal catalysis.1 Introduction2 Indole C2 Alkylation with α-Diazotized Meldrum’s Acid3 Indole C2 Alkylation with Diazomalonate Derivatives and Related Compounds4 Indole C7 Alkylation with Diazomalonates and Related Compounds5 Tandem Indole C2–H Alkylation/Cyclization6 Indoline C7 Alkylation with Diazomalonates and Related Compounds7 Tandem Indoline C7–H Alkylation/Cyclization8 Conclusion

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

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