A novel approach to the synthesis of optically pure 12aminoalkyl aziridines via a nucleophilic ringopening reaction of aziridine is presented. Preparation of a versatile precursor of novel functionalized polymers. Aziridines are a group of organic compounds sharing the aziridine functional group which is a three membered heterocycle with one amine group and two methylene groups. Synthesis and properties of bicyclic aziridines, derivatives. The synthesis and applications of nalkenyl aziridines.
Bicyclic aziridines, derivatives of 2,2,6,6tetramethyl4piperidone triacetoneamine, are synthesized, which by acids treatment undergo the nc1 or nc2 bonds cleavage to form the corresponding pyrrolines, pyrrolidines, and piperidines. It is a colorless, toxic, volatile liquid that is of significant practical interest. Aziridines are the smallest possible azaheterocycles and well known to organic chemists for their tremendous potential in the design of organic synthesis and medicinal chemistry 47. A comprehensive overview aziridines, which are threemembered nitrogen containing heterocycles, have created considerable research interest because of their fundamental and practical importance, they have been known as a class of versatile intermediates in the synthesis of different kinds of. Mar 27, 2007 dehydrochlorination of methyl 2chloroaziridine 2carboxylates generates the first examples of enantiopure 2substituted 2hazirine 3carboxylates which undergo the aza diels. The reaction takes place under mild conditions in the presence of znbr2 with moderate chemical yields. Some recent advances in the field of stereoselective synthesis of aziridines focusing on new methodologies, mechanistic insights. Aziridines are organic compounds containing the aziridine functional group, a threemembered heterocycle with one amine nr and two methylene bridges cr 2. In addition, we have expanded this concept to the synthesis of enantiomerically pure, terminal alkyl aziridines. Aziridines article about aziridines by the free dictionary. For activated aziridins ring opening is normally through s n2 at the least hindered ringcarbon and for fused bicyclic systems via furstplattner diaxial opening n h co2 r r h co2et r co 2r br nhco2et r co2r.
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 h. 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. This item appears in the following collections academic publications 176163 academic output radboud university. Epoxides can be converted into aziridines by nucleophilic attack of azide ion, the staudinger reaction, and aziridine ring. 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 properties. Ethyleneimine aziridine 151564 hazard summary ethyleneimine has many uses, including in polymerization products and in adhesives and binders. Asymmetric synthesis of 22pyridylaziridines from 2. Rethinking their application and manipulation in synthesis christopher r. The parent compound is aziridine or ethylene imine, with molecular formula c. An improved and mild wenker synthesis of aziridines article pdf available in synthesis 201009 october 2010 with 1,237 reads how we measure reads. Open access publications 51559 freely accessible full text publications. Functionalised aziridines in synthesis and catalysis. The class of aziridines are of broader interest in medicinal chemistry.
Since polyfunctional aziridines are trifunctional and the acrylic emulsion of polyurethane dispersion can be multifunctional, a crosslink density or network is formed through this reaction mechanism. Synthetic applications of nh aziridine containing compounds. Polyfunctional aziridine pz28 pz28 is a propylene imine trifunctional polyaziridine that is used in both aqueous and nonaqueous coatings, inks, and adhesives to promote both physical and chemical properties. Synthesis and nucleophilic opening of a new symmetric bis. The formation of 12aminoalkyl aziridines, starting from optically pure nh. Recent synthetic applications of chiral aziridines william mccoull,a franklin a. The aziridine end groups can react with active hydrogen as found on carboxyl. Besides many recently published ruthenium, copper, and manganese catalysts, a novel macrocyclic tetracarbene ironii catalyst promotes the synthesis of aziridines in good yields and with low catalyst loadings. Nalkyl aziridines were investigated for several reasons. Aziridines are useful intermediates in organic chemistry due to their highly strained ring systems which allow for a wide range of reactivity. The addition of chloromethyllithium to the imine derived from 2pyridinecarboxaldehyde and svalinol, protected as its otrimethylsilyl ether, gave the 1,2disubstituted aziridine with good yield and diastereoselectivity.
Synthesis and reactivity of 2 carboxymethylaziridine. Synthesis of aziridines from alkenes and aryl azides with a reusable macrocyclic tetracarbene iron catalyst. Epoxides can be converted into aziridines by nucleophilic attack of azide ion, the staudinger reaction, and aziridine ring formation with elimination of triphenylphosphine oxide. Wulffs group has developed a robust catalytic asymmetric aziridination reaction providing. 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. With the development of the catalytic asymmetric synthesis of trisubstituted aziridines presented here, it will be of interest to investigate the mechanistic di. 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. Most contemporary methods of chiral aziridine preparation have relied on the chiral pool. In a direct route for the synthesis of alkylsubstituted chiral aziridines from achiral starting materials, readily accessed allylic hydroxylamine esters undergo copper hydridecatalyzed intramolecular hydroamination with a high degree of regio and enantiocontrol to afford the aziridine products in good to excellent yields in highly. Pdf an improved and mild wenker synthesis of aziridines. Aziridines as intermediates in diversityoriented syntheses. Catalytic asymmetric synthesis of trisubstituted aziridines. Application of aziridines for the synthesis of isoquinoline. Entry r method a yield % method b yield % 1 h 46 74 2 ch 3 53 78 3 c 2h.
Alder reaction with dienes to give bicyclic and tricyclic aziridines in good yields. Besides their importance as reactive intermediates, many biologically active compounds also contain these threemembered rings. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. Aziridines are highly reactive compoundsstill several natural products are found to bear such skeleton. 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. Synthesis of aziridines from alkenes and aryl azides with. Styrenes reacted with sulfonamide in the presence of potassium carbonate and iodine in chcl 3 under visible light irradiation to produce the corresponding aziridines in good yields. Aziridines and epoxides in organic synthesis wiley. Acute shortterm inhalation exposure to ethyleneimine causes severe respiratory tract irritation and inflammation in humans, but symptoms may be delayed for several hours. Synthesis of imidazolines from aziridines by michael robert kuszpit the majority of the work in this thesis presents a new method to syntheisize imidazolines from both chiral and racemic aziridines. Short and efficient synthesis of optically active ntosyl. The geometry, energy, strain energy, and inversion barrier of 2methyleneaziridine and 2,3bismethyleneaziridine were calculated and compared with similar information on aziridine itself. Synthesis of chiral 12aminoalkylaziridines via a self. Synthesis of 2 carboxymethyl aziridines is effectuated via functional group transformations of compounds derived from the chiral pool or starting from 2formylaziridines.
Synthesis and nucleophilic opening of a new c 2 symmetric bisaziridine. The sulfates were cyclized with sodium hydroxide, and even with nonnucleophilic sodium carbonate. In this report, the potentially competitive basepromoted e2like rearrangement of aziridines to form allylic amines is investigated. A first section includes introduction part for all the subsections listed below where as second section will give more insight on the result and discussion. First synthesis of aziridines using polymersupported triphenylphosphine isabelle mccort, ste. 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. Department of chemistry, the university of tennessee, knoxville, tennessee 379961600, united states. Shaun murphreeb aemory university, atlanta, ga 30322 email.
Aziridines and azirines with exocyclic unsaturation have also been the subject of theoretical studies. Direct synthesis of s ntosyl aziridines 1 from samino alcohols 2. Threecomponent synthesis of highly functionalized aziridines. Aziridine drug information, uses, side effects, chemistry. Azaheterocyclic compounds are wellknown to have diverse types of biological activity. The analogous reaction performed on the imine derived from svaline methyl ester gave the product containing the aziridine ring and the. The parent compound of the aziridines is called aziridine or ethylene imine with molecular formula c 2 h 5 n cas 151564. Pages in category aziridines the following 15 pages are in this category, out of 15 total. Amino alcohols were converted into their hydrogen sulfates with chlorosulfonic acid. 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. Davisb aastrazeneca, mereside, alderley park, macclesfield, cheshire, sk10 4tg, uk bdepartment of chemistry, temple university, philadelphia, pa 19122. The ring opening of ntosylaziridines with trimethylsilylated nucleophiles, catalyzed by n,n,n,ntetramethylethylenediamine, led to the production of.
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