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. Synthesis of nsulfonyl aziridines through regioselective. With the potential to introduce two adjacent chiral centers with high atom economy, this methodology rightly deserves a place of prominence in synthetic organic chemistry. Stereoselective multicomponent reactions in the synthesis or. Epoxides in complex molecule synthesis aziridines and.
Acetylene chemistry chemistry, biology, and material science isbn 3527307818 2004 aziridines and epoxides in organic synthesis edited by andrei k yudin the editor andrei k yudin st george street 80 m5s 3h6. In 1996 he took up his present position as reader in biological organic chemistry at the university of reading. Onepot synthesis of aziridines from vinyl selenones and variously functionalized primary amines. Synthesis and reactivity of 2 carboxymethylaziridine. Small ring heterocycles, such as epoxides and aziridines, are present in several natural products and are also highly versatile building blocks, frequently involved in the synthesis of numerous bioactive products and pharmaceuticals. Carbonylation as a method for synthesizing organic intermediates and substrates from epoxides and aziridines venkata a.
A mild, convenient protocol for the synthesis of cisaziridines employs a catalytic amount of bronsted acid. Aziridines aziridines are the aza analogues of epoxides and are prepared by similar. Organocatalyzed enantioselective desymmetrization of. Aziridine is a saturated organic heteromonocyclic parent, a member of aziridines and an azacycloalkane. 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. Aziridines and epoxides in organic synthesis wiley online books. 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. Small ring heterocycles, such as epoxides and aziridines, are. Request pdf aziridines and epoxides in organic synthesis synthesis of vinylepoxides vinylepoxides from unfunctionalized dienes epoxidation with dioxiranesepoxidation with mnsalen.
Traditional enantioselective desymmetrizations of mesoepoxides and aziridines, as well as kinetic resolutions of racemic epoxides, have been established as highly useful processes for the synthesis of enantiopure intermediates. However, there are some difficulties that should be pointed out. Paper based on a presentation at the 16th international conference on organic synthesis. Aziridines article about aziridines by the free dictionary. Epoxides propylene oxide are one of the most commonly used gelating agents in the solgel synthesis of metal oxide e. Asymmetric synthesis of epoxides and aziridines from aldehydes and imines varinder k.
Configured cyclophellitol epoxides and aziridines sybrin p. Stereoselective multicomponent reactions in the synthesis. Yudin, aziridines and epoxides in organic synthesis, wileyvch, weinheim 2006. Aziridines and epoxides in organic synthesis request pdf. Only recent methods published in the last five years are discussed. The renowned editor has succeeded in gathering together excellent authors to cover synthesis, applications, and the biological aspects in equal depth. Their synthetic utility lies in the fact that they can be ringopened with a broad range of nucleo.
Jan 03, 2014 aziridines, the triangular, comparably highlystrained nitrogen analogues of epoxides, are important synthetic intermediates i. Organic letters trimethylsilyldiazomethane as a versatile. Azacycloalkanes from epoxides and aziridines springerlink. View the article pdf and any associated supplements and figures for a period. Aziridines, the nitrogenous analogues of epoxides, have until recently excited far less interest amongst synthetic organic chemists than their oxygenated counterparts, with some justification. The practical stereocontrolled synthesis of vicinal. Dec 05, 2019 a highly diastereoselective desymmetrization of pquinamines via regioselective ring opening of epoxides and aziridines under mild conditions has been developed.
Nonheme iron catalysts for epoxidation and aziridination. Despite the prevalence of the nh aziridine motif in bioactive natural products and the clear advantages of this unprotected parent structure over nprotected derivatives as a synthetic building block, no practical methods have emerged for direct synthesis of this compound class from unfunctionalized olefins. Application of aziridines for the synthesis of isoquinoline. Importance of epoxides in organic chemistry ome o oh o o o h o r oh r ho r o r ring opening by nucleophiles if carbonyl compounds have been said. Because of the potential for increased efficiency and selectivity, along with the advantages of environmentally benign synthetic procedures, multicomponent. Rethinking their application and manipulation in synthesis christopher r. Because of the potential for increased efficiency and selectivity, along with the advantages of environmentally benign synthetic procedures. Aziridines are highly reactive compoundsstill several natural products are found to bear such skeleton. Divided roughly equally between aziridines and epoxides, the twelve chapters discuss.
The inherent polarity coupled with ring strain makes epoxides susceptible to various reactions with different. A chairlike sixmembered transition state with minimized 1,3diaxial interactions explains the relative stereoselectivity of the cyclization reaction. Aziridines and epoxides in organic synthesis wiley. 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.
However, the enantioselective desymmetrization of meso aziridines and meso epoxides catalyzed by small chiral organic molecules has only emerged in recent years. Aziridines are useful intermediates in organic chemistry due to their highly strained ring systems which allow for a wide range of reactivity. Onepot synthesis of aziridines from vinyl selenones and. Dec 18, 2009 traditional enantioselective desymmetrizations of meso epoxides and aziridines, as well as kinetic resolutions of racemic epoxides, have been established as highly useful processes for the synthesis of enantiopure intermediates. Ringopening of cycloalkane epoxides and aziridines with. Request pdf aziridines and epoxides in organic synthesis introductionasymmetric epoxidation of carbonyl compounds aryl, vinyl, and alkyl epoxides stoichiometric ylidemediated. 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. Direct stereospecific synthesis of unprotected nh and n. Discovering effective new methods for the synthesis of aziridines and epoxides, as well as developing novel transformations of these heterocycles, has been an extremely active area of research in recent years. Silvia sternativo, francesca marini, francesca del verme, antonella calandriello, lorenzo testaferri, marcello tiecco. Aziridines and epoxides in organic synthesis, is therefore timely, since there have been no monographs on this topic in quite some time. Organic chemistry, arrhenius laboratory, stockholm university, 106 91 stockholm, sweden. Jan 09, 2006 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 parent compound is aziridine or ethylene imine, with molecular formula c 2 h 4 nh. The examples of application of azacycloalkanes in the medical and organic chemistry as biologically active substances and synthons for their preparation were. The possibility of epoxides conversion into aziridines was considered. Filling a gap in the literature, this clearly structured book. Request pdf aziridines and epoxides in organic synthesis introductionoxidants available for selective transition metalcatalyzed epoxidationepoxidations of olefins catalyzed by early. Aziridines aziridines aziridines are the aza analogues. Nikolova application of aziridines for the synthesis of isoquinoline derivatives 107 scheme 3 scheme 4 scheme 5 biologically important n. 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. Several drugs feature aziridine rings, including mitomycin c, porfiromycin, and azinomycin b carzinophilin. Aziridines and epoxides in organic synthesis by andrei k. Carbonylation as a method for synthesizing organic. Synthesis of aziridines, nucleophilic ringopening of aziridines and epoxides, organic synthesis with. The practical stereocontrolled synthesis of vicinal halohydrins and haloamines from vinyl epoxides and vinyl aziridines lukasz j.
Aziridines and epoxides in organic synthesis sigmaaldrich. Synthesis of aziridines aziridines and epoxides in. View notes aziridines from nh 2 at university of pennsylvania. A mechanism to explain this novel reaction is proposed. Valerian dragutan, ileana dragutan, albert demonceau and. Direct stereospecific synthesis of unprotected nhnme. Diastereoselective desymmetrization of pquinamines through. Undoubtedly, these synthetic methodologies will continue to demonstrate their versatile utilities in organic synthesis. Aziridines, the triangular, comparably highly strained nitrogen analogs of epoxides, are important synthetic intermediates i. Her research is currently focused on asymmetric organocatalysis, asymmetric oxidations with nonheme iron complexes and synthesis of natural product hybrids for medicinal chemistry.
Filling a gap in the literature, this clearly structured book presents the much. Regiodivergent ring opening of chiral aziridines science. An active goal in organic synthesis is to take this carbontrapped in a waste productand reuse it to build useful chemicals. It is a colorless, toxic, volatile liquid that is of significant practical interest. Besides their importance as reactive intermediates, many biologically active compounds also contain these threemembered rings. Synthesis of nsulfonyl aziridines through regioselective opening of epoxides under solidliquid ptc conditions. Two alternative and complementary onepot procedures for the direct transformation of 2amino alcohols to ntosyl aziridines are presented. Direct stereospecific synthesis of unprotected nh and nme. Widening the usefulness of epoxides and aziridines in synthesis. Request pdf aziridines and epoxides in organic synthesis introductionpreparation of aziridine2carboxylates and aziridine2phosphonates preparation of aziridine2carboxylates cyclization of.
The class of aziridines are of broader interest in medicinal chemistry. Selected examples for the synthesis of aziridines from alkenes. An amine functional group displaces the adjacent halide in an intramolecular nucleophilic substitution reaction to generate an aziridine. Aziridine is the organic compounds consisting of the threemembered heterocycle ch 2 2 nh. Epoxides the epoxides are considered versatile starting materials in organic synthesis.
Aziridines and epoxides in organic synthesis 2006 yudin. Aziridines and epoxides in organic synthesis general monograph. Theoretical study of lactone synthesis singlesite catalysts multisite catalysts o o. Aziridines and epoxides are among the most widely used intermediates in organic synthesis, acting as precursors to complex molecules due to the strains. Organocatalyzed enantioselective desymmetrization of aziridines and epoxides.
Enantioselective desymmetrization of meso aziridines and meso epoxides with various nucleophiles by organocatalysis has emerged as a cuttingedge approach in recent years. Ethyleneimine, stabilized appears as a clear colorless liquid with an ammonia like odor. The publication of this book, aziridines and epoxides in organic synthesis, is therefore timely, since there have. Combining enyne metathesis with longestablished organic transformations. Request pdf aziridines and epoxides in organic synthesis synthesis of vinylepoxides vinylepoxides from unfunctionalized dienes epoxidation with. 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. Methods of preparation of azetidines, pyrrolidines, and piperidines from epoxides and aziridines were analyzed. Less hindered aziridines can be obtained in high yields by tosylation and in situ cyclization effected by potassium hydroxide in waterdichloromethane. Unlimited viewing of the articlechapter pdf and any associated supplements and figures.
Enantioselective desymmetrization of mesoaziridines and mesoepoxides with various nucleophiles by organocatalysis has emerged as a cuttingedge approach in recent years. Aziridines are organic compounds containing the aziridine functional group, a threemembered heterocycle with one amine nr and two methylene bridges cr 2. While aziridines are present in some biologically important molecules such as mitomycins 50 and azinomycins, 51 figure 1. Using carbon dioxide as a building block in organic synthesis. The utility of epoxides, for example, in the enantioselective synthesis of oxygen. The claisen rearrangement methods and applications isbn 3527308253 2005 francois diederich, peter j stang, and rik r tikwinski eds. Zhdankin, in handbook of heterocyclic chemistry third edition, 2010. Aug 25, 2006 the renowned editor has succeeded in gathering together excellent authors to cover synthesis, applications, and the biological aspects in equal depth. Diastereoselective desymmetrization of pquinamines. A highly diastereoselective desymmetrization of pquinamines via regioselective ring opening of epoxides and aziridines under mild conditions has been developed. A reaction of a chiral aldimine derived from phenylalaninal proceeded with high diastereoselectivity. Several routes have been developed for the syntheses of aziridines aziridination. Direct transformation of epoxides to 1,2diacetates with ac2oboh3 system. 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.
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