In addition, we have expanded this concept to the synthesis of enantiomerically pure, terminal alkyl aziridines. View the article pdf and any associated supplements and figures for a period of 48 hours. A diastereo and enantioselective approach to access chiral cf 2functionalized aziridines from difluorodiazoethyl phenyl sulfone phso 2 cf 2 chn 2 and in situformed aldimines is described. Afagh master of science department of chemistry university of toronto 2010 abstract nalkenyl aziridines are a unique class of molecules that do not behave as typical enamines as a result of the inability of the nitrogen atom lonepair of electrons to delocalize. Aziridines are ubiquitous in bioactive molecules and often serve as key synthetic building blocks. Pdf aziridines are important precursors for the synthesis of various nitrogencontaining bioactive molecules, such as heterocycles, alkaloids and. This article is from beilstein journal of organic chemistry, volume 10. Aziridines ethylene imines are important building blocks in organic synthesis, because they allow for convenient access to amines, amino alcohols, diamines, and other useful nitrogencontaining molecules. This document was downloaded for personal use only. A highly regio and stereoselective synthesis of novel. Synthesis of aziridines from alkenes and aryl azides with. The base abstracts an amine proton enabling it to displace the sulfate group.
As a consequence, the preparation of aziridines is of great importance 11. Abstract synthesis of imidazolines from aziridines by michael robert kuszpit the majority of the work in this thesis presents a new method to syntheisize imidazolines. In aziridines and epoxides in organic synthesis, a. Asymmetric synthesis of cf2functionalized aziridines by.
Abstractthe coii complex of a new d2symmetric chiral porphyrin 3,5dimesqingphyrin. Alkylative ringopening of bicyclic aziridinium ion and. Aziridine is a saturated organic heteromonocyclic parent, a member of aziridines and an azacycloalkane. Although this reaction is studied by many groups, the synthesis of amino phosphonic acids is less explored. The original wenker synthesis of aziridine itself takes place in two steps. The main application of azomethine ylides in organic synthesis is based upon their potential. The catalyst, me,ettcphfencch32pf62, was synthesized from the tetraimidazolium precursor me,ettcphi4 and characterized by nmr spectroscopy, electrospray ionization mass spectrometry, and singlecrystal xray diffraction. Aziridines and epoxides in organic synthesis request pdf. A mechanism to explain this novel reaction is proposed. Preparation of polyaziridine with a defined tacticity. Synthesis and reactions of aziridines via batch and flow.
Traditional aziridine synthesis via imine activation relies heavily on the application of strong, often metalbased lewis acids, i. Ethyleneimine aziridine 151564 hazard summary ethyleneimine has many uses, including in polymerization products and in adhesives and binders. Aziridines and epoxides in organic synthesis wiley online books. Remarkably, both electronrich and electronpoor olefins are converted to aziridines with high efficiency. In the areas of medicinal chemistry and chemical biology, aziridines are of current interest as starting materials for the preparation of peptides and the synthesis of peptidelike. C cleavage of aziridines and to favor the formation of azomethine ylides. Chapter 2 gives a brief introduction to flow chemistry, and describes the synthesis of aziridines from 1,2amino alcohols, as well as their subsequent. Acute shortterm inhalation exposure to ethyleneimine causes severe respiratory tract irritation and inflammation in humans, but symptoms may be delayed for several hours. This iron complex catalyzes the aziridination of electron.
We report herein an intramolecular kitbhp mediated oxidative dehydrogenative csp3h amination reaction to synthesize a diverse array of trans2,3disubstituted aziridines in good yields under mild conditions. Synthesis of aziridines from imines and ethyl diazoacetate. Media in category aziridines the following 41 files are in this category, out of 41 total. This thesis describes the synthesis and ring opening reactions of aziridines performed under batch as well as continuous flow conditions. A new iron aziridination catalyst supported by a macrocyclic tetracarbene ligand has been synthesized. Synthetic applications of nh aziridine containing compounds shannon marie decker master of science department of chemistry university of toronto 2010 abstract unprotected nh aziridine aldehydes are surprisingly stable compounds which can undergo reactions in the absence of protecting groups. Besides their importance as reactive intermediates, many biologically active compounds also contain these threemembered rings. Aziridines can be prepared in organic synthesis in several ways. Synthesis and reactivity of 2 carboxymethylaziridine. Threecomponent synthesis of highly functionalized aziridines. Conversion of aziridines to oxazolidines through geminal. Butler september 16, 2004 introduction aziridines 1 have been synthetic targets as well as useful building blocks in synthesis since gabriels 1888 discovery of the smallest nitrogen containing heterocycle. The intramolecular nucleophilic substitution reactions methods ia and ii involve attack of a nucleophilic amino. Because it easily forms imines, its primary use is in the modification of latex surfacecoating resins to.
Cycloaddition of tertiary aziridines and carbon dioxide. Increased angle strain in aziridine is also responsible for increased barrier for nitrogen inversion. Catalytic asymmetric synthesis of alkynyl aziridines. This method allowed carboncarbon bond formation of nonactivated aziridine via aziridinium ion ringopening in regio and stereo.
Synthesis of chiral organocatalysts derived from aziridines. Azetidines and aziridines through nickelcatalyzed cross. A simple protocol for the synthesis of dihydrobenzothiazines through regio. Author links open overlay panel wei sun chungu xia hongwang wang. The synthesis and applications of nalkenyl aziridines. Pdf aziridines are important precursors for the synthesis of various nitrogen containing bioactive molecules, such. Widening the usefulness of epoxides and aziridines in synthesis in. Pdf a novel approach to the synthesis of optically pure 12aminoalkyl aziridines via a nucleophilic. Aziridine moieties occur in many natural products and are also encountered in unnatural biologically active compounds including drugs in clinical use, especially in the field of cancer treatment.
The reaction of ntosyl imines with in situ generated iodomethyllithium, with a simple and rapid experimental protocol, allows an efficient and general synthesis of aziridines. Wulffs group has developed a robust catalytic asymmetric aziridination. The key steps include the regio and diastereocontrolled nucleophilic ringopening of these threemembered heterocycles followed by mild reductive cyclization of the. Most contemporary methods of chiral aziridine preparation have relied on the chiral pool. Synthesis of aziridines from imines and ethyl diazoacetate in room temperature ionic liquids. Chapter 1 gives a brief introduction to the synthesis and ring opening reactions of aziridines. This barrier is high enough for the isolation of separate invertomers for instance the cis and trans invertomers of nchloro2methylaziridine. A synthetic route to chiral dihydrobenzothiazines through.
Aziridines article about aziridines by the free dictionary. Alkylative ringopening of bicyclic aziridinium ion generated from 4hydroxybutylaziridine with organocopper reagent was achieved successfully to afford 2alkylsubstituted piperidine in high or moderate yield. Aziridine is the organic compounds consisting of the threemembered heterocycle ch 2 2 nh. Aziridines and epoxides in organic synthesis wiley. Unlimited viewing of the articlechapter pdf and any associated. Amino acid synthesis by aziridine ring opening reaction is a good example to the use of aziridines. A reaction of a chiral aldimine derived from phenylalaninal proceeded with high diastereoselectivity. Azaheterocyclic compounds are wellknown to have diverse types of biological activity. Direct transformation of epoxides to 1,2diacetates with ac2oboh3 system aziridines are useful intermediates in organic chemistry due to their highly strained ring systems which allow for a wide range of reactivity. The journal of organic chemistry 2008, 73 23, 94119416. If the inline pdf is not rendering correctly, you can download the pdf file here. Aziridines and epoxides are among the most widely used intermediates in organic synthesis, acting as precursors to complex molecules due to the strains incorporated in their skeletons. The synthesis and applications of nalkenyl aziridines nicholas a.
The observed excellent yields, regioselectivities and enantioselectivities find no rivals in other organocatalytic aziridine synthesis. Synthesis of 3methoxyazetidines via an aziridine to. N cyclization in excellent yields up to 95 % with high diastereo. Nikolova application of aziridines for the synthesis of isoquinoline derivatives 106 the toxicity of aziridine derivatives will depend on its own structure and activity whilst sharing the general characteristics of the aziridine group. Furthermore, intramolecular reactions and addition reactions are subdivided with respect to the mechanism of these reactions. Synthesis of 1,3oxazolidines from aziridines only a. Among them, azacyclopropanes, commonly referred as aziridines, occupy a prominent place in synthetic organic and medicinal chemistry due to its occurrence in natural resources, complexity involved in synthesis due to ringstrain, building blocks in organic synthesis, and its biological. Conversion of aziridines to oxazolidines through geminal difunctionalization of vinyl arenes or by tandem ringopeningclosing reaction of aziridine itself. Synthesis of 2aminomethylaziridines and their microwave.
Ecological information ecological data for aziridine, 2methyl bioaccumulation does not bioaccumulate. Aziridines are highly useful compounds as building blocks for the synthesis of important organic compounds. Synthetic applications of nh aziridine containing compounds. Synthesis of chiral nphosphoryl aziridines through. Synthesis of 3methoxyazetidines via an aziridine to azetidine rearrangement and theoretical rationalization of the reaction. Crosslinking mechanisms polyaziridine pa often causes allergic reactions this still widely used crosslinking principle, introduced in the late 1970s, is based on the use of a multifunctional aziridine compound synthesized from either trimethylolpropane triacrylate or pentaerithrytol tetraacrylate and ethyleneimine or propyleneimine. General procedures for the synthesis of ndiphenylphosphinyl vinyl aziridines.
Jessing 1 n r activated aziridines r co2r, so2r and cor nonactivated aziridines r h, alkyl and aryl ho nh2 o so nh 2 o o n h aziridines can be synthesized in numerous ways including sn2 displacement, 14 addition, addition of carbenes, electrophiles, nitrenes and reduction. A straightforward synthesis of aziridines is reported from electronrich azides, electrondeficient olefins, and triflic acid in cold acetonitrile. Imidazolium2carboxylates derived from nheterocyclic carbenes nhcs and co2 serve as efficient catalysts for co2carboxylation of tertiary aziridines bearing various substituents such as halogens, ether, olefin, ester, acetal, and nitro groups on the aziridine ring in 2propanol, leading to 3substituted. Yudin, aziridines and epoxides in organic synthesis, wileyvch, weinheim 2006. This salt is then reacted with sodium hydroxide in the second step forming aziridine. Volume 44, issue 11, 10 march 2003, pages 24092411. Ethyleneimine, stabilized appears as a clear colorless liquid with an ammonia like odor. Synthesis of 3methoxyazetidines via an aziridine to azetidine rearrangement and theoretical rationalization of the reaction mechanism. Rethinking their application and manipulation in synthesis christopher r. Studies have been made on the possible synthesis of 1 arylethynylaziridines by oxidative condensation of phenylacetylene with aziridine and by alkylation of aziridine with 1halo2arylacetylenes. Pdf synthesis of chiral 12aminoalkylaziridines via a self. A general strategy for the synthesis of enantiomerically pure. Drosophila melanogaster carcinogenicity rat, malefemale, oral, 28 weeks, daily positive 12. The formation of 12aminoalkylaziridines, starting from optically pure nhaziridines, occurs.
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