Rhodiumiicatalyzed 1,3dipolar cycloaddition reactions. Pdf reactivity of asymmetric benzocondensed diazines. This chapter intends to provide the reader a current state of asymmetric 1,3dipolar cycloaddition. Recent advances in the catalytic asymmetric 1,3dipolar cycloaddition of azomethine ylides javier adrio and juan c. Pdf reactivity of asymmetric benzocondensed diazines with. Asymmetric 1,3dipolar cycloaddition reactions of azomethine. Cycloaddition reactions are among the most powerful methods for the synthesis of complex compounds. Under appropriate reaction conditions with a cu i or ag i catalyst either the exo or the endo adduct was obtained with high stereoselectivity. The most common atoms4 incorporated in the 1,3dipole are nitrogen, carbon, oxygen or sulfur. This chapter intends to provide the reader a current state of asymmetric 1, 3 dipolar cycloaddition.
Chiral asymmetric 1, 3 dipolar cycloaddition reactions of azomethine ylides can be achieved by three different strategies employing either. The asymmetric synthesis of cf 3 containing spiropyrrolidin3,2oxindole through the organocatalytic 1, 3dipolar cycloaddition reaction. In this process, the regio and stereochemical 1,3dipolar cycloaddition of azomethine ylides, which were generated insitu by the reaction of isatin derivatives and sarcosin. Asymmetric 1,3dc reactions with azomethine imines and.
If the 6membered cyclic dielsalder transition state can be considered as benzenelike, then 1,3dipolar cycloadditions are cyclopentadienide like. Asymmetric 1,3dipolar cycloaddition reaction of nitrones. The reactivity of asymmetric benzocondensed diazines in the 1, 3 dipolar cycloaddition reactions with nitrilimines was investigated. Pilar lamata, a ricardo rodriguez, a maria carmona, a luis a. Asymmetric 1,3dipolar cycloaddition reactions between. Request pdf on jan 1, 2003, staffan karlsson and others published asymmetric 1,3dipolar cycloaddition reactions of azomethine ylides, thiocarbonyl ylides, and nitrones. Chiral, nonracemic lewis bases and lewis acids have been employed as catalysts for these reactions, which may or may not occur through pericyclic reaction mechanisms. Here a lone pair replaces one of the double bonds of the diene 4electron component. A muoxotype chiral bistiiv oxide s,s1 can be successfully utilized in the asymmetric 1,3dipolar cycloaddition reactions between various nitrones 2 and acrolein to give the corresponding isoxazolidines with high to. Asymmetric 1,3dipolar cycloaddition reactions chemical. Asymmetric 1,3dipolar cycloaddition reactions catalyzed.
Pericyclic reactions and organic photochemistry 2,204 views. The earliest 1, 3 dipolar cycloadditions were described in the late 19th century to the early 20th century, following the discovery of 1, 3 dipoles. The three most important types of cycloaddition reactions that occur by concerted reaction mechanisms are. Huisgen 1,3dipolar cycloaddition organic chemistry portal. Particularly, 1,3dipolar cycloaddition 1,3dc is a classic reaction of a 1,3dipole i with a dipolarophile ii, such as alkenes, alkynes, and molecules possessing. Asymmetric cascade 1,3dipolar cycloaddition reactions of imines. Asymmetric 1,3dipolar reactions of cyclic vinyl ptolyl. Moreover, enantioselective dipolar cycloaddition reaction versions allow for the creation of several adjacent stereogenic centres in a single step with stereochemical control.
Nonstandard experimental conditions can often enhance organocatalytic reactions considerably. Here a lone pair replaces one of the double bonds of the diene 4. Asymmetric 1,3dipolar cycloaddition reactions of nitrile oxides catalyzed by chiral binaphthyldiimineniii complexes hiroyuki suga, yuki adachi, kouhei fujimoto, yasuhisa furihata, teruko tsuchida, akikazu kakehi and toshihide baba. This process provides efficient access to highly enantiomerically enriched 4. Enantioselective coppercatalyzed 1,3dipolar cycloadditions. This has been accomplished by using asymmetric intermolecular 1,3dipolar cycloaddition reactions of azomethine ylides, thiocarbonyl ylides and nitrones. Department of chemistry and central laboratory of the institute of molecular technology for drugdiscovery and synthesis, hong kong baptist university, kowloon. If the 6membered cyclic dielsalder transition state can be considered as benzenelike, then 1, 3 dipolar cycloadditions are cyclopentadienide like. Synthetic applications of 1,3dipolar cycloaddition chemistry toward.
Asymmetric 1,3dipolar cycloaddition reaction of nitrones and. Reaction of 2,4dienals with nitrones allows for a highly regio and stereoselective 1,3dipolar cycloaddition in the presence of an aminocatalyst. Alkenyl arenes as dipolarophiles in catalytic asymmetric 1. Cycloaddition reactions 1 are a fundamental class of processes in synthetic chemistry and among them 1,3dipolar cycloadditions are atomeconomic transformations that permit the construction of fivemembered heterocycles. Asymmetric 1,3dipolar cycloaddition using fesulphos sigma.
Pericyclic reactions 2 cycloaddition reactions diel. The reactivity of asymmetric benzocondensed diazines in the 1,3dipolar cycloaddition reactions with nitrilimines was investigated. Aug 01, 2016 1, 3 dipolar cycloaddition reactions pericyclic reactions and organic photochemistry. Asymmetric 1,3dipolar cycloaddition reactions between enals and nitrones catalysed by halfsandwich rhodium or iridium diphosphane complexes ainara asenjo, a fernando viguri, a m. The first cycloaddition on the remote olefin can be followed either by a cascade reaction or. The journal of organic chemistry 2009, 74 3, 109911. When the alkyne is converted to a copper acetylide prior to cycloaddition, ring contraction occurs to produce a.
General procedure b for asymmetric 1,3dipolar cycloaddition of azomethine ylides with alkylidene malonates catalyzed by agirtfbiphamphos complex in the presence of k2co3 as base under argon atmosphere rtfbiphamphos 1e6. In summary, the 1, 3 dipolar cycloaddition allows the production of various 5membered heterocycles. Asymmetric 1, 3 dipolar cycloaddition reactions of azomethine ylides offer an effective means. Moreover, this study further documents that chiral amines can be employed as asymmetric catalysts for a range of transformations that traditionally utilize metal salts. Chiral asymmetric 1,3dipolar cycloaddition reactions of azomethine ylides can be achieved by three different strategies employing either. The addition of a 1,3dipole to an alkene for the synthesis of fivemembered rings is a classic reaction in organic chemistry. All three approaches have been suecessfully implemented by our group. Apr 27, 2015 1, 3 dipolar cycloaddition or huisgen cycloaddition cycloaddition pericyclic reaction. The antiapproach with respect to the tolyl group, and the exoarrangement of the dipole are clearly favored on steric grounds.
Asymmetric 1,3dipolar cycloaddition using fesulphos. The influence of ionic liquids, highpressure conditions, ultrasound, microwave irradiation and ball. Request pdf on jan 1, 2003, staffan karlsson and others published asymmetric 1,3dipolar cycloaddition reactions of azomethine ylides, thiocarbonyl ylides, and nitrones find, read and cite all. Outline formation of substituted pyrrolidines through 1, 3 dipolar cycloaddition of azomethine ylides. The 1,3dipolar cycloaddition reaction provides a powerful method for the synthesis of fivemembered heterocyclic rings. A chiral tiiv catalyst can be successfully utilized in the asymmetric 1,3dipolar cycloaddition reactions between various nitrones and acrolein to give the corresponding endo cycloadducts isoxazolidines with high to excellent enantioselectivities.
Metal complexes versus organocatalysts in asymmetric 1,3dipolar. The journal of organic chemistry 1998, 63 10, 348485. The 1,3dipolar cycloaddition of the nitrone with the metal acetylide affords a 5membered ring that rearranges to form a. Dipolar cycloaddition reactions of enones by primary amine catalysis we report herein a 1,3. The antiapproach with respect to the tolyl group, and the exoarrangement of. Pdf asymmetric lewis acidcatalyzed 1,3dipolar cycloadditions. The corresponding chiral multisubstituted spiroisoxazolidines with three contiguous quaternarytertiary stereocenters were obtained in moderate to high.
In the presence of a copper complex, derived from cuotf2 and bisoxazoline, a series of hydropyrrolobenzazole derivatives containing quaternary stereogenic centers were obtained in high yields with excellent enantioselectivity. Methacrylonitrile and nitrones catalysed by welldefined. The dielsalder reaction is the best known of the cycloaddition reactions. Asymmetric cascade 1,3dipolar cycloaddition reactions of. Assessment of nonstandard reaction conditions for asymmetric. Copperiibisoxazoline catalyzed asymmetric 1,3dipolar. Cycloaddition reactions results in the formation of a new ring. Metal ion catalysed asymmetric 1,3dipolar cycloaddition reactions of imines of. Alkenyl arenes as dipolarophiles in catalytic asymmetric 1,3.
An efficient, onepot, fourcomponent procedure for the synthesis of a small library of new chiral spiro oxindolopyrrolidines with high regio, diastereo 99. In summary, the 1,3dipolar cycloaddition allows the production of various 5membered heterocycles. Synthesis of carboxylated pyrrolidine derivatives via 1,3dipolar cycloadditions of homochiral doublestabilised eazomethine ylids. Introduction of chirality through chiral vinyl sulfinyloxides. Catalytic enantioselective 1,3dipolar cycloadditions of. Highly enantioselective 1, 3 dipolar cycloaddition reactions of several 1, 3 dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and. Enantiomerically enriched 1,2p,nbidentate ferrocenyl. Recent advances in the catalytic asymmetric 1,3dipolar. Azomethine ylides are commonly used as dipoles for the synthesis. Nov 11, 2016 the use of alkenyl arenes as dipolarophiles in the catalytic asymmetric 1,3. Abstract a chiral tiiv catalyst can be successfully utilized in the asymmetric 1, 3 dipolar cycloaddition reactions between various nitrones and acrolein to give the corresponding endo cycloadducts isoxazolidines with high to excellent enantioselectivities.
Asymmetric 1, 3 dipolar cycloadditions pellissier, h. To our knowledge, this is the first example of an organocatalytic 1,3dipolar cycloaddition. This approach toward asymmetric syntheses is of major importance in both the pharmaceutical and agricultural industries. This method, known as the kinugasa reaction, is an alternative to keteneimine cycloaddition. Pdf highly tuned, onepoint binding chiral iron and ruthenium complexes. Sung and hee reported an enantioselective synthesis of the. In particular, the development and application of the 1, 3 dipolar cycloaddition, an important member of this reaction class, has grown immensely due to its powerful ability to efficiently build various fivemembered heterocycles. Outline formation of substituted pyrrolidines through 1,3dipolar cycloaddition of azomethine ylides. The 1,3dipolar cycloaddition reaction is among the most prominent reactions in organic synthesis. Highly enantioselective 1,3dipolar cycloaddition reactions of several 1,3dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and. The regio and stereoselective control of cycloaddition reactions to polyconjugated systems has been demonstrated by applying asymmetric organocatalysis. Catalytic asymmetric ketene cycloadditions establish four or sixmembered rings via the formal cycloaddition of a nucleophilic ketene or vinylketene with an electrophilic two or fouratom. Asymmetric 1,3dipolar cycloaddition reactions between enals. Asymmetric 1,3dipolar cycloaddition reactions of nitrile oxides catalyzed by chiral binaphthyldiimineniii complexes.
Asymmetric 1,3dipolar cycloaddition reaction between a,b. Asymmetric 1,3dipolar cycloaddition reactions catalyzed by. Dipolar cycloaddition reactions of enones by primary amine catalysis qi yang key laboratory for molecular recognition and function institute of chemistry, beijing, 100190, university of chinese academy of sciences, beijing, china, 100490. The 1, 3 dipolar cycloaddition is a chemical reaction between a 1, 3 dipole and a dipolarophile to form a fivemembered ring. Synthetic applications of 1, 3dipolar cycloaddition. Asymmetric 1,3dipolar cycloadditions pellissier, h. The results demonstrated that, at variance with the symmetric quinoxaline, a certain grade of diastereoselectivity. This reaction is a 1,3dipolar cycloaddition, in which the nitrone acts as the 1,3dipole, and the alkene or alkyne as the dipolarophile. Recent approach to functionalized 2,5dihydropyrroles. Synthetic applications of 1,3dipolar cycloaddition chemistry toward heterocycles and natural products provides a comprehensive, current reference for the synthesis of complex molecules based on cycloaddition reactions.
Asymmetric 1,3dipolar cycloaddition reactions of azomethine imines with acrolein catalyzed by lproline and its derivatives. Asymmetric 1,3dipolar cycloaddition reactions of nitrile. Many reactions can be performed with high regioselectivity and even enantioselective transformations of prochiral substrates have been published. Pdf intramolecular 1,3dipolar cycloaddition reactions in targeted.
Asymmetric 1, 3 dipolar cycloaddition reactions of nitrile oxides catalyzed by chiral binaphthyldiimineniii complexes. Controlling asymmetric remote and cascade 1,3dipolar. Among the wide variety of organic asymmetric syntheses, cycloadditions are highly attractive processes which allow the construction of several new stereogenic centers with stereochemical control in a single step. Asymmetric 1,3dipolar cycloaddition reactions between methacrylonitrile and nitrones catalysed by welldefined mdiphosphane m rh, ir complexes author links open overlay panel daniel carmona fernando viguri ainara asenjo pilar lamata fernando j. The use of alkenyl arenes as dipolarophiles in the catalytic asymmetric 1,3.
The current study explores the effectiveness of a range of nonstandard reaction conditions for the asymmetric organocatalytic 1,3dipolar cycloaddition of a nitrone with. Asymmetric 1, 3 dipolar cycloaddition reactions of nitrile oxides catalyzed by chiral binaphthyldiimineniii complexes hiroyuki suga, yuki adachi, kouhei fujimoto, yasuhisa furihata, teruko tsuchida, akikazu kakehi and toshihide baba. Regioselectivie synthesis of new spiro oxindolopyrrolidines. Recent advances in the catalytic asymmetric 1, 3dipolar. Particularly, 1,3dipolar cycloaddition 1,3dc is a classic reaction of a 1,3 dipole i with a dipolarophile ii, such as alkenes, alkynes, and molecules possessing. Carretero catalytic asymmetric 1,3dipolar cycloadditions of azomethine ylides have turned out to be one of the most e. Catalytic asymmetric ketene cycloadditions organic reactions. In particular, the development and application of the 1,3dipolar cycloaddition, an important member of this reaction class, has grown immensely due to its powerful ability to efficiently build various fivemembered heterocycles. In particular, the 1,3dipolar cycloaddition reaction dcr constitutes an efficient approach for the preparation of fivemembered. In particular, the 1, 3 dipolar cycloaddition reaction dcr constitutes an efficient approach for the preparation of fivemembered. Asymmetric 1,3dipolar cycloaddition of azomethine ylides. Some interesting examples may be found in the recent literature.