Synthesis and reactivities of monofluoro acylboronates in chemoselective amide bond forming ligation with hydroxylamines

2016 ◽  
Vol 14 (1) ◽  
pp. 16-20 ◽  
Author(s):  
Hidetoshi Noda ◽  
Jeffrey W. Bode
Keyword(s):  
Bioorganic Chemistry ◽  
Amide Bond ◽  
Chemical Ligation ◽  
Bond Forming

Synthesis and reactivities of monofluoroacylboronates are described in the context of bioorganic chemistry and chemical ligation.

Are Aminomethyl Thioesters Viable Intermediates in Native Chemical Ligation Type Amide Bond Forming Reactions?

2018 ◽  
Vol 71 (9) ◽  
pp. 697
Author(s):  
Carlie L. Charron ◽  
Jade M. Cottam Jones ◽  
Craig A. Hutton
Keyword(s):  
Amide Bond ◽  
Native Chemical Ligation ◽  
Direct Reaction ◽  
Chemical Ligation ◽  
Bond Forming ◽  
Type Process ◽  
Bond Forming Reactions ◽  
Subsequent Conversion ◽  
Three Component Coupling

The condensation of N-mercaptomethyl amines and thioesters is a potential route to amides, via aminomethyl thioester intermediates, in a native chemical ligation type process followed by self-cleavage of the ‘mercaptomethyl’ auxiliary. This paper describes investigations towards the preparation of aminomethyl thioesters, and subsequent conversion into amides, from a three-component coupling of formaldehyde, a thioacid, and an amine. Our studies suggest that while such intermediates may be formed en route to amides, no advantages are offered over the direct reaction of the amine and thioacid precursors.

scholarly journals Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yunyun Ning ◽  
Shuaishuai Wang ◽  
Muzi Li ◽  
Jie Han ◽  
Chengjian Zhu ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Functional Group ◽  
Amide Bond ◽  
Coupling Reagents ◽  
Complex Molecules ◽  
Bond Forming ◽  
Synergistic Catalysis ◽  
Wide Range ◽  
Amidation Reaction ◽  
Forming Methods

AbstractDevelopment of catalytic amide bond-forming methods is important because they could potentially address the existing limitations of classical methods using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction of carboxylic acids with nitroarenes and nitroalkanes enabled by the triplet synergistic catalysis of FeI2, P(V)/P(III) and photoredox catalysis, which avoids the production of byproducts from stoichiometric coupling reagents. A wide range of carboxylic acids, including aliphatic, aromatic and alkenyl acids participate smoothly in such reactions, generating structurally diverse amides in good yields (86 examples, up to 97% yield). This Umpolung amidation strategy opens a method to address challenging regioselectivity issues between nucleophilic functional groups, and complements the functional group compatibility of the classical amidation protocols. The synthetic robustness of the reaction is demonstrated by late-stage modification of complex molecules and gram-scale applications.

scholarly journals Minimizing HCN in DIC/Oxyma-Mediated Amide Bond-Forming Reactions

2020 ◽  
Vol 24 (7) ◽  
pp. 1341-1349 ◽  
Author(s):  
Marion Erny ◽  
Marika Lundqvist ◽  
Jon H. Rasmussen ◽  
Olivier Ludemann-Hombourger ◽  
Frédéric Bihel ◽  
...  
Keyword(s):  
Amide Bond ◽  
Bond Forming ◽  
Bond Forming Reactions

scholarly journals The reactivity of an unusual amidase may explain colibactin’s DNA cross-linking activity

2019 ◽  
Author(s):  
Yindi Jiang ◽  
Alessia Stornetta ◽  
Peter W. Villalta ◽  
Matthew R. Wilson ◽  
Paul D. Boudreau ◽  
...  
Keyword(s):  
Pathogenic Bacteria ◽  
Amide Bond ◽  
Bond Forming ◽  
Interstrand Cross Links ◽  
Cross Links ◽  
Dna Crosslinking ◽  
Alkylate Dna ◽  
Link Formation

ABSTRACTCertain commensal and pathogenic bacteria produce colibactin, a small molecule genotoxin that causes interstrand cross-links in host cell DNA. Though colibactin has been found to alkylate DNA, the molecular basis for cross-link formation is unclear. Here, we report that the colibactin biosynthetic enzyme ClbL is an amide bond-forming enzyme that links aminoketone and β-keto thioester substrates in vitro and in vivo. The substrate specificity of ClbL strongly supports a role for this enzyme in terminating the colibactin NRPS-PKS assembly line. This transformation would incorporate two electrophilic cyclopropane warheads into the final natural product scaffold. Overall, this work provides a biosynthetic explanation for colibactin’s DNA crosslinking activity and paves the way for further study of its chemical structure.

scholarly journals SEA Ligation Is Accelerated at Mildly Acidic pH. Application to the Formation of Difficult Peptide Junctions

2019 ◽  
Author(s):  
Marine Cargoet ◽  
Vincent Diemer ◽  
Laurent Raibaut ◽  
Elizabeth Lissy ◽  
Benoît Snella ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Peptide Bond ◽  
Native Chemical Ligation ◽  
Acidic Ph ◽  
Chemical Ligation ◽  
Bond Forming ◽  
Neutral Ph ◽  
Wide Range ◽  
Peptide Segments ◽  
Model Peptides

The bis(2-sulfanylethyl)amido (SEA)-mediated ligation has been introduced in 2010 as a novel chemoselective peptide bond forming reaction. SEA ligation is a useful reaction for protein total synthesis that is complementary to the native chemical ligation (NCL). In particular, SEA ligation proceeds efficiently in a wide range of pH, from neutral pH to pH 3-4. Thus, the pH can be chosen to optimize the solubility of the peptide segments or final product. It can be also chosen to facilitate the formation of difficult junctions, since the rate of SEA ligation increases significantly by decreasing the pH from 7.2 to 4.0. Here we describe a protocol for SEA ligation at pH 5.5 in the presence of 4-mercaptophenylacetic acid (MPAA) or at pH 4.0 in the presence of a newly developed diselenol catalyst. The protocols describe the formation of a valyl-cysteinyl peptide bond between two model peptides.<br>

scholarly journals The Problem of Aspartimide Formation During Protein Chemical Synthesis Using SEA-Mediated Ligation

2019 ◽  
Author(s):  
Jennifer Bouchenna ◽  
Magalie Sénéchal ◽  
Hervé Drobecq ◽  
Jérôme Vicogne ◽  
Oleg Melnyk
Keyword(s):  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Side Reaction ◽  
Peptide Bond ◽  
Protein Targets ◽  
Chemical Ligation ◽  
Phase Synthesis ◽  
Bond Forming ◽  
Aspartimide Formation ◽  
Peptide Segments

Aspartimide formation often complicates the solid phase synthesis of peptides. Much less discussed is the potential occurrence of this side-reaction during the coupling of peptide segments using chemoselective peptide bond forming reactions such as the native chemical ligation and extended methods. Here we describe how to manage this problem using bis(2-sulfenylethyl)amido (SEA)-mediated ligation and SUMO-2/SUMO-3 as protein targets.<br>

Amide Synthesis by Transamidation of Primary Carboxamides

Synthesis ◽  
2020 ◽  
Vol 52 (21) ◽  
pp. 3231-3242
Author(s):  
Sylvain Laclef ◽  
Maria Kolympadi Marković ◽  
Dean Marković
Keyword(s):  
Synthetic Methods ◽  
Amide Bond ◽  
Industrial Chemistry ◽  
Bronsted Acid ◽  
Brønsted Acid ◽  
Atom Economy ◽  
Bond Forming ◽  
Effective Strategies ◽  
Brönsted Acid ◽  
Metal Catalyzed

The amide functionality is one of the most important and widely used groups in nature and in medicinal and industrial chemistry. Because of its importance and as the actual synthetic methods suffer from major drawbacks, such as the use of a stoichiometric amount of an activating agent, epimerization and low atom economy, the development of new and efficient amide bond forming reactions is needed. A number of greener and more effective strategies have been studied and developed. The transamidation of primary amides is particularly attractive in terms of atom economy and as ammonia is the single byproduct. This review summarizes the advancements in metal-catalyzed and organocatalyzed transamidation methods. Lewis and Brønsted acid transamidation catalysts are reviewed as a separate group. The activation of primary amides by promoter, as well as catalyst- and promoter-free protocols, are also described. The proposed mechanisms and key intermediates of the depicted transamidation reactions are shown.1 Introduction2 Metal-Catalyzed Transamidations3 Organocatalyzed Transamidations4 Lewis and Brønsted Acid Catalysis5 Promoted Transamidation of Primary Amides6 Catalyst- and Promoter-Free Protocols7 Conclusion

Sign in / Sign up

Export Citation Format

Share Document