Copper Iodide-Catalyzed Coupling Reaction of Benzofuran-3(2H)-ones with Amines: an Approach to α-Ketoamides

2021 ◽  
Author(s):  
Rongxiang Chen ◽  
Ruo-Ling Jia ◽  
Wenbo Li ◽  
Wei Zhao ◽  
Kai-Kai Wang ◽  
...  
Keyword(s):  
Formation Mechanism ◽  
Bond Cleavage ◽  
Direct Synthesis ◽  
Bond Formation ◽  
Coupling Reaction ◽  
Copper Iodide

A CuI-catalyzed coupling reaction of benzofuran-3(2H)-ones with amines has been well established for the direct synthesis of α-ketoamides. This process involves C–O bond cleavage and C=O/C–N bond formation. Mechanism studies...

I2/TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C–C Bond Cleavage

Synlett ◽  
2017 ◽  
Vol 28 (15) ◽  
pp. 2018-2023 ◽  
Author(s):  
Xiang Fang ◽  
Xueyan Yang ◽  
Tongle Shao ◽  
Jun Zhou ◽  
Chen Jin ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Coupling Reaction ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Oxidation Pathway ◽  
Keto Esters ◽  
Oxidative Coupling Reaction

A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I2/TBHP promoted sequential iodination, C–C bond cleavage, C–O bond formation and oxidation pathway is involved in this reaction.

α-Ketophosphonates in the Synthesis of α-iminophosphonates

2020 ◽  
Vol 7 (2) ◽  
pp. 226-238
Author(s):  
Petro P. Ony`sko ◽  
Tetyana I. Chudakova ◽  
Vladimir V. Pirozhenko ◽  
Alexandr B. Rozhenko
Keyword(s):  
Bond Cleavage ◽  
Direct Synthesis ◽  
Equilibrium Mixture ◽  
Primary Amines ◽  
Alkyl Amines ◽  
Protic Solvents ◽  
Metallic Salts ◽  
Direct Preparation ◽  
Stage Synthesis ◽  
Aprotic Dipolar Solvent

The potentialities of condensation of α-ketophosphonates with primary amines for direct synthesis of α-iminophosphonates have been revealed. Diesters of α-ketophosphonic acids react with the primary amines by two competitive pathways: with a formation of α-iminophosphonates or a C-P bond cleavage resulting in a hydrogen phosphonate and an acylated amine. In many cases, the latter undesirable pathway is dominant, especially for more nucleophilic alkyl amines. Using metallic salts of α-ketophosphonates avoids the C-P bond cleavage, allowing direct preparation of α-phosphorylated imines by the reaction with primary amines. This strategy provides an atom economy single-stage synthesis of iminophosphonates – precursors of bio relevant phosphorus analogs of α-amino acids. Methyl sodium iminophosphonates, bearing aryl or heteryl substituents at the imino carbon atom exist in solutions at room temperature as an equilibrium mixture of Z- and E-isomers. A configuration of the C=N bond can be controlled by the solvent: changing the aprotic dipolar solvent DMSO-d6 by water or alcohols leads to the change from a predominant Z-isomer to almost an exclusive E-form. In contrast, diesters of the respective iminophosphonates exist in non-protic solvents predominantly in Econfiguration. The solvent effect on E-Z stereochemistry is demonstrated by DFT calculations.

scholarly journals N–N Bond Formation between Primary Amines and Nitrosos: Direct Synthesis of 2-Substituted Indazolones with Mechanistic Insights

2018 ◽  
Vol 20 (16) ◽  
pp. 4736-4739 ◽  
Author(s):  
Jie S. Zhu ◽  
Niklas Kraemer ◽  
Marina E. Shatskikh ◽  
Clarabella J. Li ◽  
Jung-Ho Son ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Bond Formation ◽  
Primary Amines

Pyrrolizinone‐Fused BOPYINs: Characterization and Selective C‐O Bond Formation Mechanism

2021 ◽  
Vol 6 (31) ◽  
pp. 7894-7900
Author(s):  
Cong Hu ◽  
Liu Wen ◽  
Xi Chen ◽  
Jiaying Yan ◽  
Kaibo Zheng ◽  
...  
Keyword(s):  
Formation Mechanism ◽  
Bond Formation
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