Azides – Diazonium Ions – Triazenes: Versatile Nitrogen-rich Functional Groups

2014 ◽  
Vol 67 (3) ◽  
pp. 328 ◽  
Author(s):  
Dominik K. Kölmel ◽  
Nicole Jung ◽  
Stefan Bräse
Keyword(s):  
Functional Groups ◽  
Combinatorial Chemistry ◽  
Chemical Biology ◽  
Mitsunobu Reaction ◽  
Staudinger Ligation ◽  
Sandmeyer Reaction ◽  
Huisgen Reaction ◽  
Diazonium Ions ◽  
Synthetic Routes ◽  
Pschorr Reaction

For more than 100 years, nitrogen-rich compounds such as azides, diazonium ions, and triazenes have proved to be extremely valuable. Because these functional groups can be easily introduced into various substrates, they are frequently used nowadays. More importantly, they can be converted into a great number of other functional groups. The scope of this article is thus to summarize possible synthetic routes for the formation of these functional groups as well as to highlight some of the most prominent applications of these exciting moieties in chemical biology and combinatorial chemistry. Many of the most famous name reactions such as the Staudinger reduction, Staudinger ligation, Sandmeyer reaction, Wallach reaction, Mitsunobu reaction, Huisgen reaction, Balz–Schiemann reaction, Meerwein arylation, Pschorr reaction or Gomberg–Bachmann reaction are covered.

Sustainable Flow Synthesis of Encoded Beads for Combinatorial Chemistry and Chemical Biology

2018 ◽  
Vol 20 (8) ◽  
pp. 492-498 ◽  
Author(s):  
Hongxia Hu ◽  
Sergei Nikitin ◽  
Adam Bjørnholdt Berthelsen ◽  
Frederik Diness ◽  
Sanne Schoffelen ◽  
...  
Keyword(s):  
Combinatorial Chemistry ◽  
Chemical Biology ◽  
Flow Synthesis

The Staudinger Ligation—A Gift to Chemical Biology

2004 ◽  
Vol 43 (24) ◽  
pp. 3106-3116 ◽  
Author(s):  
Maja Köhn ◽  
Rolf Breinbauer
Keyword(s):  
Chemical Biology ◽  
Staudinger Ligation

scholarly journals Synthesis of chiral anti-1,2-diamine derivatives through copper(I)-catalyzed asymmetric α-addition of ketimines to aldimines

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Xu-Cheng Gan ◽  
Cheng-Yuan Zhang ◽  
Feng Zhong ◽  
Ping Tian ◽  
Liang Yin
Keyword(s):  
Nitro Group ◽  
Functional Groups ◽  
Phenyl Group ◽  
Asymmetric Reactions ◽  
Bioactive Molecules ◽  
Sandmeyer Reaction ◽  
Aryl Amine ◽  
Common Structure ◽  
Group A ◽  
High Yields

Abstract Chiral 1,2-diamines serve as not only common structure units in bioactive molecules but also useful ligands for a range of catalytic asymmetric reactions. Here, we report a method to access anti-1,2-diamine derivatives. By means of the electron-withdrawing nature of 2- or 4-nitro-phenyl group, a copper(I)-catalyzed asymmetric α-addition of ketimines derived from trifluoroacetophenone and 2- or 4-NO2-benzylamines to aldimines is achieved, which affords a series of chiral anti-1,2-diamine derivatives in moderate to high yields with moderate to high diastereoselectivity and high to excellent enantioselectivity. Aromatic aldimines, heteroaromatic aldimines, and aliphatic aldimines serve as suitable substrates. The nitro group is demonstrated as a synthetical handle by several transformations, including a particularly interesting Fe(acac)3-catalyzed radical hydroamination with a trisubstituted olefin. Moreover, the aryl amine moiety obtained by the reduction of the nitro group serves as a synthetically versatile group, which leads to the generation of several functional groups by the powerful Sandmeyer reaction, such as -OH, -Br, -CF3, and -BPin.

scholarly journals Synthetic approaches to multifunctional indenes

2011 ◽  
Vol 7 ◽  
pp. 1739-1744 ◽  
Author(s):  
Neus Mesquida ◽  
Sara López-Pérez ◽  
Immaculada Dinarès ◽  
Ermitas Alcalde
Keyword(s):  
Functional Groups ◽  
Lithium Salt ◽  
Condensation Process ◽  
Type Reaction ◽  
Synthetic Routes ◽  
Synthetic Approaches

The synthesis of multifunctional indenes with at least two different functional groups has not yet been extensively explored. Among the plausible synthetic routes to 3,5-disubstituted indenes bearing two different functional groups, such as the [3-(aminoethyl)inden-5-yl)]amines, a reasonable pathway involves the (5-nitro-3-indenyl)acetamides as key intermediates. Although several multistep synthetic approaches can be applied to obtain these advanced intermediates, we describe herein their preparation by an aldol-type reaction between 5-nitroindan-1-ones and the lithium salt of N,N-disubstituted acetamides, followed immediately by dehydration with acid. This classical condensation process, which is neither simple nor trivial despite its apparent directness, permits an efficient entry to a variety of indene-based molecular modules, which could be adapted to a range of functionalized indanones.

Rapid in Situ Generation of Benzene Diazonium Ions under Basic Aqueous Conditions from Bench-Stable Triazabutadienes

Synlett ◽  
2017 ◽  
Vol 28 (14) ◽  
pp. 1767-1770
Author(s):  
Jie He ◽  
Flora Kimani ◽  
John Jewett
Keyword(s):  
Functional Groups ◽  
Large Degree ◽  
Π Interactions ◽  
Diazonium Ions ◽  
Degree Of Stability ◽  
Acidic Conditions ◽  
In Situ Generation ◽  
Aqueous Conditions ◽  
Benzene Diazonium

Aryl diazonium ions are useful across a range of chemical/biochemical areas. These species are generally made using strongly acidic conditions, which can be detrimental to acid-sensitive functional groups. The ability to generate benzene diazonium ions under basic aqueous conditions is reported herein along with newfound understanding on the aqueous reactivity of solubilized triazabutadienes whereby π-interactions appear to confer a large degree of stability.

Radical Fluorosulfonylation: Accessing Alkenylsulfonyl Fluorides from Alkenes and Alkynes

Synlett ◽  
2021 ◽  
Author(s):  
Xingliang Nie ◽  
Saihu Liao
Keyword(s):  
Drug Discovery ◽  
Chemical Biology ◽  
Research Interest ◽  
High Demand ◽  
The Past ◽  
Synthetic Routes

Sulfonyl fluorides have widespread applications in many fields. In particular, the increasing research interest on the study of sulfonyl fluorides in the context of chemical biology and drug discovery in the past decade has raised a high demand for new and efficient methods for the synthesis of sulfonyl fluorides. Even though many synthetic routes have been developed in recent years, the corresponding radical fluorosulfonylation remains elusive. Here, we report our efforts toward to this goal, and the identification of sulfuryl chlorofluoride (FSO2Cl) as an effective fluorosulfonyl radical precursor, as well as the development of radical fluorosulfonylation of alkenes and radical trans chloro/fluorosulfonylation of alkynes.

The Staudinger Ligation — A Gift to Chemical Biology

ChemInform ◽  
2004 ◽  
Vol 35 (34) ◽  
Author(s):  
Maja Koehn ◽  
Rolf Breinbauer
Keyword(s):  
Chemical Biology ◽  
Staudinger Ligation

scholarly journals Current Synthetic Routes to Peptidyl Mono-Fluoromethyl Ketones (FMKs) and Their Applications

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5601
Author(s):  
Carissa M. Lloyd ◽  
Neil Colgin ◽  
Steven L. Cobb
Keyword(s):  
Protease Inhibitors ◽  
Chemical Biology ◽  
Medicinal Chemistry ◽  
Biologically Active ◽  
Solution Phase ◽  
Chemical Probes ◽  
Cellular Processes ◽  
Synthetic Routes

Peptidyl mono-fluoromethyl ketones (FMKs) are a class of biologically active molecules that show potential as both protease inhibitors for the treatment of a range of diseases and as chemical probes for the interrogation of cellular processes. This review describes the current solid- and solution-phase routes employed for the synthesis of peptidyl mono-FMKs. In addition, it provides a brief overview of some of the key applications of FMKs in the fields of chemical biology and medicinal chemistry.

Sign in / Sign up

Export Citation Format

Share Document