Topic
1,3-Dipolar cycloaddition
About: 1,3-Dipolar cycloaddition is a research topic. Over the lifetime, 5560 publications have been published within this topic receiving 98615 citations.
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TL;DR: This chapter covers core aspects of the strain-promoted reaction of cycloalkynes with azides, as well as tools to achieve further reaction acceleration by means of modulation ofcycloalkyne structure, nature of azide, and choice of solvent.
Abstract: A nearly forgotten reaction discovered more than 60 years ago—the cycloaddition of a cyclic alkyne and an organic azide, leading to an aromatic triazole—enjoys a remarkable popularity. Originally discovered out of pure chemical curiosity, and dusted off early this century as an efficient and clean bioconjugation tool, the usefulness of cyclooctyne–azide cycloaddition is now adopted in a wide range of fields of chemical science and beyond. Its ease of operation, broad solvent compatibility, 100 % atom efficiency, and the high stability of the resulting triazole product, just to name a few aspects, have catapulted this so-called strain-promoted azide–alkyne cycloaddition (SPAAC) right into the top-shelf of the toolbox of chemical biologists, material scientists, biotechnologists, medicinal chemists, and more. In this chapter, a brief historic overview of cycloalkynes is provided first, along with the main synthetic strategies to prepare cycloalkynes and their chemical reactivities. Core aspects of the strain-promoted reaction of cycloalkynes with azides are covered, as well as tools to achieve further reaction acceleration by means of modulation of cycloalkyne structure, nature of azide, and choice of solvent.
251 citations
TL;DR: In this article, a series of catalysts have been applied for both the normal electron-demand and inverse electronic demand 1,3-dipolar cycloaddition reaction of nitrones with electron-deficient and electron-rich alkenes, respectively.
246 citations
TL;DR: The reaction of N-vinylimidazole and diazo compounds derived from aldehydes gave exclusively 3-substituted pyrazoles in a one-pot process.
Abstract: A convenient one-pot procedure for the preparation of pyrazoles by 1,3-dipolar cycloaddition of diazo compounds generated in situ has been developed. Diazo compounds derived from aldehydes were reacted with terminal alkynes to furnish regioselectively 3,5-disubstituted pyrazoles. Furthermore, the reaction of N-vinylimidazole and diazo compounds derived from aldehydes gave exclusively 3-substituted pyrazoles in a one-pot process.
246 citations
TL;DR: In this article, a straightforward strategy is proposed for the derivatization of poly(e-caprolactone) (PCL) by statistical copolymerization of α-chloro-e-CAPOLACTone (αCleCL) with e-CAPCL (eCL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP).
Abstract: A straightforward strategy is proposed for the derivatization of poly(e-caprolactone) (PCL). First, statistical copolymerization of α-chloro-e-caprolactone (αCleCL) with e-caprolactone (eCL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendent chlorides were converted into azides by reaction with sodium azide. Finally, duly substituted terminal alkynes were reacted with pendent azides by copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, thus a “click” reaction. According to this strategy, pendent hydroxyl and acrylate groups and atom transfer radical polymerization (ATRP) initiators were successfully attached to PCL. Similarly, amphiphilic graft copolymers were prepared by cycloaddition of an alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents of the copolyester. The dependence of the grafting yield on the experimental conditions of the “click” reaction, i.e., temperature, solvent, and catalyst, was investigated. This strategy is very versatile be...
243 citations
TL;DR: The history of this research area is presented, important older reports are highlighted, and the evolution and further development of the concept of 1,3‐dipolar cycloadditions are described.
Abstract: The concept of 1,3-dipolar cycloadditions was presented by Rolf Huisgen 60 years ago. Previously unknown reactive intermediates, for example azomethine ylides, were introduced to organic chemistry and the (3+2) cycloadditions of 1,3-dipoles to multiple-bond systems (Huisgen reaction) developed into one of the most versatile synthetic methods in heterocyclic chemistry. In this Review, we present the history of this research area, highlight important older reports, and describe the evolution and further development of the concept. The most important mechanistic and synthetic results are discussed. Quantum-mechanical calculations support the concerted mechanism always favored by R. Huisgen; however, in extreme cases intermediates may be involved. The impact of 1,3-dipolar cycloadditions on the click chemistry concept of K. B. Sharpless will also be discussed.
239 citations