α-Csp3–H bond functionalization of simple ethers in radical reactions

Synthesis ◽  
2021 ◽  
Author(s):  
Yanping Feng ◽  
Xiajuan Ye ◽  
Dayun Huang ◽  
Sheng-rong Guo
Keyword(s):  
Radical Addition ◽  
Radical Reactions ◽  
Bond Functionalization ◽  
Unsaturated Compounds ◽  
Metal Catalyzed

The direct α-Csp3-H functionalization of simple ethers has emerged as one of the vital strategies among radical reactions. This review discusses their applications according to the starting materials: (1) reactions with alkenes or alkynes. (2) reactions with other unsaturated compounds. (3) reactions with nucleophilic partners. Mechanisms like radical addition, elimination, oxidation, metal-catalyzed coupling, C-H activation, cyclization and rearrangement will be discussed herein.

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 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.

Visible-light-facilitated P-center radical addition to C=X (X = C, N) bonds results in cyclizations

2021 ◽  
Author(s):  
Shang-Dong Yang ◽  
Chong Li ◽  
Juan Wang
Keyword(s):  
Visible Light ◽  
Organophosphorus Compounds ◽  
Radical Addition ◽  
Radical Reactions

Visible-light-facilitated phosphorus radical reactions have been developed as a powerful and sustainable tool for the synthesis of various organophosphorus compounds. In general, these reactions require stoichiometric amounts of oxidants, and...

scholarly journals Applications of transition metal catalyzed P-radical for synthesis of organophosphorus compounds

2019 ◽  
Vol 91 (1) ◽  
pp. 87-94 ◽  
Author(s):  
Wei Ren ◽  
Qiang Yang ◽  
Shang-Dong Yang
Keyword(s):  
Transition Metal ◽  
Recent Work ◽  
Organic Synthesis ◽  
Organophosphorus Compounds ◽  
Powerful Method ◽  
Unsaturated Compounds ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Abstract Phosphorus-radical participated difunctionalization reactions with unsaturated compounds have been recognized as powerful method for organic synthesis. This review covers our recent work on the application of transition metal catalyzed P-radical promoted difunctionalization for synthesis of organophosphorus compounds.

Highly Diastereoselective Radical Reactions of Substituted Methylideneimidazolidinones and Related Systems

2004 ◽  
Vol 57 (7) ◽  
pp. 629 ◽  
Author(s):  
George A. Adamson ◽  
Athelstan L. J. Beckwith ◽  
Christina L. L. Chai
Keyword(s):  
Radical Addition ◽  
Radical Reactions

Stannane-mediated radical addition to methylideneimidazolidinones occurs with good to excellent diastereo-selectivity. The stereochemical outcome of addition is highly dependent on the nature of the N1 substituent on the imidazolidinone ring.

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