N-Acylsuccinimides: twist-controlled, acyl-transfer reagents in Suzuki–Miyaura cross-coupling by N–C amide bond activation

2017 ◽  
Vol 15 (42) ◽  
pp. 8867-8871 ◽  
Author(s):  
Yuki Osumi ◽  
Chengwei Liu ◽  
Michal Szostak
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Amide Bond ◽  
Acyl Transfer ◽  
Palladium Catalyzed

The palladium-catalyzed Suzuki–Miyaura cross-coupling of N-acylsuccinimides as versatile acyl-transfer reagents via selective amide N–C bond cleavage is reported.

Nickel-Catalyzed Negishi Cross-Coupling of N-Acylsuccinimides: Stable, Amide-Based, Twist-Controlled Acyl-Transfer Reagents via N–C Activation

Synthesis ◽  
2017 ◽  
Vol 49 (16) ◽  
pp. 3602-3608 ◽  
Author(s):  
Michal Szostak ◽  
Shicheng Shi
Keyword(s):  
Bond Cleavage ◽  
Cross Coupling ◽  
Cost Effective ◽  
Amide Bond ◽  
Acyl Transfer ◽  
Reaction Proceeds ◽  
Bond Distortion ◽  
Metal Catalyzed ◽  
Half Twist ◽  
Broad Interest

This paper reports a room temperature, nickel-catalyzed Negishi cross-coupling of N-acylsuccinimides with arylzinc reagents via selective N–C bond cleavage enabled by amide bond twist. The reaction proceeds using a commercially available, air-stable Ni(II) precatalyst in the absence of additives under exceedingly mild conditions. Of broad interest, this report introduces N-acylsuccinimides as stable, crystalline, electrophilic, cost-effective, benign, amide-based acyl transfer reagents via acyl metal intermediates. The reaction selectivity is governed by half-twist of the amide bond in N-acylsuccinimides, thus opening the door for applications in metal-catalyzed manifolds via redox­-neutral reaction pathways tuneable by amide bond distortion.

ChemInform Abstract: Palladium-Catalyzed Cross-Coupling of Aryl Fluorides with N-Tosylhydrazones via C-F Bond Activation.

ChemInform ◽  
2015 ◽  
Vol 46 (52) ◽  
pp. no-no
Author(s):  
Haiqing Luo ◽  
Guojiao Wu ◽  
Shuai Xu ◽  
Kang Wang ◽  
Chaoqiang Wu ◽  
...  
Keyword(s):  
Bond Activation ◽  
Cross Coupling ◽  
Palladium Catalyzed

Palladium-Catalyzed/Lewis Acid-Promoted Alkene Dimerization and Cross-Coupling with AlcoholsviaCH Bond Activation

2008 ◽  
Vol 350 (4) ◽  
pp. 552-556 ◽  
Author(s):  
Yi-Jun Jiang ◽  
Yong-Qiang Tu ◽  
En Zhang ◽  
Shu-Yu Zhang ◽  
Ke Cao ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Bond Activation ◽  
Cross Coupling ◽  
Palladium Catalyzed

Palladium-catalyzed C(carbonyl)–C bond cleavage of amides: a facile access to phenylcarbamate derivatives with alcohols

2018 ◽  
Vol 54 (62) ◽  
pp. 8606-8609 ◽  
Author(s):  
Xufei Yan ◽  
Huihui Sun ◽  
Haifeng Xiang ◽  
Da-Gang Yu ◽  
Daibing Luo ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Palladium Catalyzed ◽  
Sulfur Containing

A sulfur-containing auxiliary enabled palladium-catalyzed C(carbonyl)–C bond activation of amides was reported to form phenylcarbamate derivatives with alcohols.

Palladium-catalyzed C–S bond activation and functionalization of 3-sulfenylindoles and related electron-rich heteroarenes

2017 ◽  
Vol 4 (8) ◽  
pp. 1590-1594 ◽  
Author(s):  
Jianxiao Li ◽  
Yanni An ◽  
Jiawei Li ◽  
Shaorong Yang ◽  
Wanqing Wu ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Palladium Catalyzed

A novel palladium-catalyzed approach for constructing functionalized heteroarenes via C–S bond cleavage and C–C bond formation has been demonstrated.

scholarly journals Well-Defined Pre-Catalysts in Amide and Ester Bond Activation

Molecules ◽  
2019 ◽  
Vol 24 (2) ◽  
pp. 215 ◽  
Author(s):  
Sandeep R. Vemula ◽  
Michael R. Chhoun ◽  
Gregory R. Cook
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Ester Bond ◽  
Coupling Reactions ◽  
Catalytic Systems ◽  
Design And Synthesis ◽  
Cross Coupling Reactions ◽  
Made In

Over the past few decades, transition metal catalysis has witnessed a rapid and extensive development. The discovery and development of cross-coupling reactions is considered to be one of the most important advancements in the field of organic synthesis. The design and synthesis of well-defined and bench-stable transition metal pre-catalysts provide a significant improvement over the current catalytic systems in cross-coupling reactions, avoiding excess use of expensive ligands and harsh conditions for the synthesis of pharmaceuticals, agrochemicals and materials. Among various well-defined pre-catalysts, the use of Pd(II)-NHC, particularly, provided new avenues to expand the scope of cross-coupling reactions incorporating unreactive electrophiles, such as amides and esters. The strong σ-donation and tunable steric bulk of NHC ligands in Pd-NHC complexes facilitate oxidative addition and reductive elimination steps enabling the cross-coupling of broad range of amides and esters using facile conditions contrary to the arduous conditions employed under traditional catalytic conditions. Owing to the favorable catalytic activity of Pd-NHC catalysts, a tremendous progress was made in their utilization for cross-coupling reactions via selective acyl C–X (X=N, O) bond cleavage. This review highlights the recent advances made in the utilization of well-defined pre-catalysts for C–C and C–N bond forming reactions via selective amide and ester bond cleavage.

Non-Classical Amide Bond Formation: Transamidation and Amidation of Activated Amides and Esters by Selective N–C/O–C Cleavage

Synthesis ◽  
2020 ◽  
Vol 52 (18) ◽  
pp. 2579-2599 ◽  
Author(s):  
Michal Szostak ◽  
Guangchen Li
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Amide Bond ◽  
Acyl Transfer ◽  
Metal Free ◽  
Amide Bond Formation ◽  
New Methods ◽  
Formidable Challenge ◽  
Tetrahedral Intermediates

In the past several years, tremendous advances have been made in non-classical routes for amide bond formation that involve transamidation and amidation reactions of activated amides and esters. These new methods enable the formation of extremely valuable amide bonds via transition-metal-catalyzed, transition-metal-free, or metal-free pathways by exploiting chemoselective acyl C–X (X = N, O) cleavage under mild conditions. In a broadest sense, these reactions overcome the formidable challenge of activating C–N/C–O bonds of amides or esters by rationally tackling nN → π*C=O delocalization in amides and nO → π*C=O donation in esters. In this account, we summarize the recent remarkable advances in the development of new methods for the synthesis of amides with a focus on (1) transition-metal/NHC-catalyzed C–N/C–O bond activation, (2) transition-metal-free highly selective cleavage of C–N/C–O bonds, (3) the development of new acyl-transfer reagents, and (4) other emerging methods.1 Introduction2 Transamidation of Amides2.1 Transamidation by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)2.2 Transition-Metal-Free Transamidation via Tetrahedral Intermediates2.3 Reductive Transamidation2.4 New Acyl-Transfer Reagents2.5 Tandem Transamidations3 Amidation of Esters3.1 Amidation of Esters by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)3.2 Transition-Metal-Free Amidation of Esters via Tetrahedral Intermediates3.3 Reductive Amidation of Esters4 Transamidations of Amides by Other Mechanisms5 Conclusions and Outlook

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