scholarly journals Diverse secondary C(sp3)–H bond functionalization via site-selective trifluoroacetoxylation of aliphatic amines

2018 ◽  
Vol 9 (30) ◽  
pp. 6374-6378 ◽  
Author(s):  
Yongzhen Tang ◽  
Yuman Qin ◽  
Dongmei Meng ◽  
Chaoqun Li ◽  
Junfa Wei ◽  
...  
Keyword(s):  
Aliphatic Amine ◽  
Aliphatic Amines ◽  
Coinage Metal ◽  
Bond Functionalization ◽  
Metal Catalyzed ◽  
Site Selective

A coinage-metal-catalyzed site-selective trifluoroacetoxylation of remote secondary C(sp3)–H bonds for aliphatic amine substrates was developed.

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

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>

Coinage Metal Catalyzed C−H Bond Functionalization of Hydrocarbons

2008 ◽  
Vol 108 (8) ◽  
pp. 3379-3394 ◽  
Author(s):  
M. Mar Díaz-Requejo ◽  
Pedro J. Pérez
Keyword(s):  
Coinage Metal ◽  
Bond Functionalization ◽  
Metal Catalyzed

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

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>

scholarly journals The Programmed Multiple C–H Bond Functionalization of 4-Hydroxyquinoline and Its Medicinal Potential

2021 ◽  
Author(s):  
Quentin Ronzon ◽  
Wei Zhang ◽  
Nicolas Casaretto ◽  
Elizabeth Mouray ◽  
Isabelle Florent ◽  
...  
Keyword(s):  
Carbonyl Group ◽  
Multiple Site ◽  
Fries Rearrangement ◽  
Bond Functionalization ◽  
Chemical Libraries ◽  
Biologically Relevant ◽  
Directing Group ◽  
Metal Catalyzed ◽  
Site Selective

<p>The introduction of substituents on bare heterocyclic scaffolds can selectively be achieved by directed C–H functionalization. However, such methods have only occasionally been used, in an iterative manner, to decorate various positions of a medicinal scaffold to build chemical libraries. We herein report the multiple, site selective, metal-catalyzed C–H functionalization of a "programmed" 4-hydroxyquinoline. This medicinally privileged template indeed possesses multiple reactive sites for diversity-oriented functionalization, of which four were targeted. The C-2 and C-8 decorations were directed by an <i>N</i>-oxide, before taking benefit of an <i>O</i>-carbamoyl protection at C-4 to perform a Fries rearrangement and install a carboxamide at C-3. This also released the carbonyl group of 4-quinolones, the ultimate directing group to functionalize position 5. Our study highlights the power of multiple C–H functionalization to generate diversity in a biologically relevant library, after showing its strong antimalarial potential.</p>

scholarly journals N-Benzo[c][1,2,5]thiazol-4-yl-3-trifluoromethylbenzamide

Molbank ◽  
10.3390/m1075 ◽  
2019 ◽  
Vol 2019 (3) ◽  
pp. M1075 ◽  
Author(s):  
Hamad H. Al Mamari ◽  
Nasser Al Awaimri ◽  
Yousuf Al Lawati
Keyword(s):  
1H Nmr ◽  
Elemental Analysis ◽  
13C Nmr ◽  
Title Compound ◽  
Structural Motif ◽  
Spectroscopic Methods ◽  
Bond Functionalization ◽  
Directing Group ◽  
Metal Catalyzed

The title compound, N-benzo[c][1,2,5]thiazol-4-yl-3-trifluoromethylbenzamide (1) was synthesized by reacting 3-trifluoromethylbenzoyl chloride (4) and 4-aminobenzo[c][1,2,5]thiadiazole (5). The compound was characterized by various spectroscopic methods (1H NMR, 13C NMR, IR, GC-MS) and its composition confirmed by elemental analysis. The importance of this compound lies in its possession of an N,N-bidentate directing group. Such a structural motif is potentially suitable for metal-catalyzed C-H bond functionalization reactions.

Highly Site-Selective Direct C−H Bond Functionalization of Unactivated Arenes with Propargyl α‑Aryl-α-diazoacetates via Scandium Catalysis

2021 ◽  
Author(s):  
Balu S. Navale ◽  
Debasish Laha ◽  
Subhrashis Banerjee ◽  
Kumar Vanka ◽  
Prof. Dr. Ramakrishna G. Bhat
Keyword(s):  
The Novel ◽  
Bond Functionalization ◽  
Site Selective

<p>Highly chemo- and regio-selective C–H bond functionalization of unactivated arenes with propargyl <i>α</i>-aryl-<i>α</i>-diazoacetates is developed using scandium catalysis. Variety of unactivated, mildly deactivated and electronically activated arenes are functionalized using this protocol. We have explored the novel combination of scandium triflate and propargyl <i>α</i>-aryl-<i>α</i>-diazoacetate as catalyst-reagent system for the effective C–H bond functionalization. The protocol avoids the use of expensive catalysts and practicality of the protocol has been demonstrated by the gram scale synthesis of very useful <i>α</i>-diarylacetates including antispasmodic drug-adephenine.</p>

Sign in / Sign up

Export Citation Format

Share Document