Positive shift in corrole redox potentials leveraged by modest β-CF3-substitution helps achieve efficient photocatalytic C–H bond functionalization by group 13 complexes

2019 ◽  
Vol 48 (32) ◽  
pp. 12279-12286 ◽  
Author(s):  
Xuan Zhan ◽  
Pinky Yadav ◽  
Yael Diskin-Posner ◽  
Natalia Fridman ◽  
Mahesh Sundararajan ◽  
...  

Tris- and tetrakis-β-trifluoromethylated gallium (3CF3-Ga, 4CF3-Ga) and aluminum (3CF3-Al, 4CF3-Al) corrole systems were synthesized by a facile “one-pot” approach and studied in the context of photocatalytic C–H bond activation.

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>


Synlett ◽  
2021 ◽  
Author(s):  
Habibur Rahaman ◽  
Brindaban Roy ◽  
Somjit Hazra ◽  
Biplab Mondal

Abstract: A one pot direct synthesis of xanthine and uric acid derivates is reported. This simple yet efficient methodology illustrates concurrent formation of two C-N bonds using CuBr2 as catalyst and one of those C-N bonds is formed by uracil C6-H bond activation.


Synthesis ◽  
2021 ◽  
Author(s):  
Tamao Ishida ◽  
Zhenzhong Zhang ◽  
Haruno Murayama ◽  
Eiji Yamamoto ◽  
Makoto Tokunaga

The C–H functionalization has been extensively studied as a direct C–C bond forming reaction with high atomic efficiency. The efforts have also been made on the reaction using supported catalysts, which are superior in terms of catalyst separation from the reaction mixture and reusability. In this review, an overview of the C–H functionalization reactions, especially for Pd and Au supported catalysts will be described. In particular, we discuss reaction mechanisms, active species, leaching, reusability, etc. 1 Introduction 2 Types of supported metal catalysts and their active species 3 Modes of C–H bond activation 4 Oxidative C–H C–H coupling of aryl compounds 5 C–H C–H coupling where one side is aromatic 6 C–H acylation of aromatic compounds and related reactions 7 Conclusion


2006 ◽  
Vol 118 (17) ◽  
pp. 2832-2834 ◽  
Author(s):  
Yoichiro Kuninobu ◽  
Yuta Nishina ◽  
Makoto Shouho ◽  
Kazuhiko Takai

2018 ◽  
Vol 83 (22) ◽  
pp. 14195-14202 ◽  
Author(s):  
Elina Ausekle ◽  
Peter Ehlers ◽  
Alexander Villinger ◽  
Peter Langer

ChemInform ◽  
2015 ◽  
Vol 46 (24) ◽  
pp. no-no
Author(s):  
Hanjie Mo ◽  
Dingben Chen ◽  
Lingzhen Xu ◽  
Di Chen ◽  
Fuyuo Pan ◽  
...  

1989 ◽  
Vol 67 (11) ◽  
pp. 1708-1710 ◽  
Author(s):  
Zaihui Zhang ◽  
T. L. Thomas Hui ◽  
Chris Orvig

A series of tris(3-hydroxy-2-methyl-4-pyridinonato)metal(III) and tris(3-hydroxy-6-hydroxymethyl-4-pyridinonato)metal(III) complexes have been prepared in water by one-pot synthesis directly from maltol and kojic acid, respectively, and the metal ion (M = Al, Ga, In) with an appropriate amine. The pyridinones have substituents at the ring nitrogen atom (CH3, C2H5). The tris(3-hydroxy-4-pyronato)metal(III) complexes are formed insitu and these undergo nucleophilic attack by the primary amine; the appropriate tris(3-hydroxy-4-pyridinonato)metal(III) complexes are obtained. This method bypasses the sequential syntheses of ligand and metal complex, and has improved the yields of the tris(ligand)metal complexes, in particular by making them much more easily accessible. The electronic effects of binding the pyrone to the metal ions and of the substituents on the pyrone ring on the reactivity are discussed. Keywords: 3-hydroxy-4 pyridinone complexes, group 13 metal ions, one-pot synthesis.


Tetrahedron ◽  
2014 ◽  
Vol 70 (38) ◽  
pp. 6717-6722 ◽  
Author(s):  
Xian-chun Tan ◽  
Ying Liang ◽  
Fang-ping Bao ◽  
Heng-shan Wang ◽  
Ying-ming Pan

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