Asymmetric palladiumcatalyzed reactions for the synthesis of pyrrolidines and other heterocycles by duy n. In this study, new short asymmetric syntheses of these two important c2symmetrical nitrogen heterocycles have been accomplished employing economically available lprolinol derivative 10 as the. Jan 18, 2019 catalytic asymmetric synthesis of arylpyrrolidines and benzo. Ring opening reactions of nitrogen heterocycles iopscience. The cycloaddition reactions have been applied in the synthesis of carbocycles and heterocycles. Asymmetric synthesis of unsaturated monocyclic and bicyclic nitrogen heterocycles. The important requirement for approval of a new drug, in case it happens to be chiral, that both enantiomers of the drug be studied in detail, have focused the attention of synthetic organic and medicinal chemists on the development of new methods for catalytic asymmetric synthesis especially of relevant saturated nheterocycles. Schindler on the development of new methods towards the synthesis of nitrogen heterocycles. Asymmetric synthesis of nitrogen heterocycles pdf free. Asymmetric synthesis of n,oheterocycles via enantioselective iridiumcatalysed intramolecular allylic amidation depeng zhao, martnfanan. Despite the success of chirally modified transitionmetal catalysts in asymmetric synthesis, in the form of the nobel prize in chemistr y in 2001, the field of asymmetric organic synthesis has since then been dominated by. Catalytic asymmetric synthesis of arylpyrrolidines and.
Divergent synthesis of fivemembered nitrogen heterocycles via cascade reactions of 4arylfuroxans. Asymmetric palladiumcatalyzed reactions for the synthesis of. The yield was determined by isolation after chromatographic purification. The asymmetric synthesis of nitrogen heterocycles is of continuing interest to medicinal and bioorganic chemistry. Asymmetric synthesis of n,oheterocycles via enantioselective iridiumcatalysed intramolecular allylic amidation depeng zhao, a martin fananasmastral, a muchieh chang, a edwin otten a and ben l.
Stepefficient asymmetric approaches to saturated nitrogen. Asymmetric synthesis of three and fourmembered ring heterocycles giuliana cardillo, luca gentilucci and alessandra tolomelli 1. The important requirement for approval of a new drug, in case it happens to be chiral, that both enantiomers of the drug be studied in detail, have focused the attention of synthetic organic and medicinal chemists on the development of new methods for catalytic asymmetric synthesis especially of relevant saturated n heterocycles. A palladiumcatalyzed cyclization reaction for the modular synthesis of highly substituted piperazines and related bis nitrogen heterocycles couples two of the carbons of a propargyl unit with various diamine components to provide products in very good yields with high regio and stereochemical control. Catalytic asymmetric synthesis of a nitrogen heterocycle through. The synthesis of chiral nitrogen containing saturated heterocycles has attracted the attention of organic chemists worldwide. The book is clearly structured, and divided into two sections asymmetric synthesis of heterocycles containing only one nitrogen and that of those with more than one nitrogen as a heteroatom such that the necessary information may be found at a glance. Importance of catalytic asymmetric synthesis of saturated n. Asymmetric synthesis of tetrazole and dihydroisoquinoline. Samariumii iodide smi 2, kagans reagent has been widely used to forge challenging cc bonds through reductive coupling reactions. Although isocyanidebased multicomponent reactions were proven to be simple, elegant and facile strategies for the synthesis of highly valuable nitrogen. The synthesis of nitrogencontaining heterocycles is important due to the fact that many biologically active molecules contain these motifs.
Asymmetric synthesis of nitrogen heterocycles wiley. Gareth rowlands of the university of sussex reports tetrahedron lett. As a result, the development of new, convenient and more efficient processes to nheterocycles is of great interest to synthetic chemists. If you continue using our site without changing your browser settings, well assume that you agree to our use of cookies.
Nitrogenbearing rings are very common features in the molecular structures of modern drugs. The resulting benzoxazine derivatives were further transformed into challenging chiral n,oketals. Nitrogen heterocycles represent vital structural motifs in biologicallyactive natural products and pharmaceuticals. Asymmetric synthesis of unsaturated monocyclic and bicyclic. Recent advances in the asymmetric synthesis of pharmacology. Nitrogencontaining heterocycles bearing pyrrole, pyrrolizine, pyrrolidine. Part one describes in four chapters asymmetric synthesis of nitrogen heterocycles containing only one heteroatom in 3,4,5,6,7 and more membered rings. Synthesis of nitrogenated heterocycles by asymmetric transfer. Asymmetric synthesis of unsaturated monocyclic and. Davis, bin yang, jiang deng, and junyi zhang department of chemistry, temple university, philadelphia, pa 19122 email. Pdf synthesis of optically active heterocyclic compounds using pd. Reactions that can modify these n heterocycles selectively are thus especially useful to optimize pharmaceutical properties.
Volume 39, issue 17, 23 april 1998, pages 25152518. Asymmetric synthesis of nitrogen heterocycles pdf free download. Using this transformation, the asymmetric synthesis of chiral nitrogen. Part two consists of four chapters covering the asymmetric synthesis of nitrogen heterocycles with more than one heteroatom. Here, all aspects of the topic are presented in a compact manner. Catalytic asymmetric addition of grignard reagents to. Synthesis of chiral nitrogen heterocycles via the narasaka. Synthesis of n heterocycles organic chemistry portal. Although isocyanidebased multicomponent reactions were proven to be simple, elegant and facile strategies for the synthesis of highly valuable nitrogen containing heterocycles, their asymmetric. Due to their rich chemical reactivity, nitro compounds play significant roles as building blocks in the synthesis of nheterocycles. Asymmetric synthesis of nitrogen heterocycles by reaction of chiral. Synthesis of nitrogenated heterocycles by asymmetric. A palladiumcatalyzed cyclization reaction for the modular synthesis of highly substituted piperazines and related bisnitrogen heterocycles couples two of the carbons of a propargyl unit with various diamine components to provide products in very good yields with high regio and stereochemical control. The aim being to convert enantiomers into diastereomers.
Asymmetric synthesis of nitrogen heterocycles by reaction. The efficient asymmetric synthesis of nitrogen heterocycles including the quinolizidine alkaloid epimyrtine, indolizidine alkaloids 209b and 223a, and agelastatin a using easily prepared sulfiniminederive chiral building blocks is described. The international team of authors provides important experimental. Stepefficient asymmetric approaches to saturated nitrogen heterocycles stepefficient asymmetric approaches to saturated nitrogen heterocycles an iminoaldol reaction between phenyl chlorovalerate and a variety of stert butylsulfinimines was developed which gave consistently high diastereoselectivites of up to 95. C2symmetric semicorrins 1, a class of bidentate nitrogen ligands specifically designed for enantioselective ca talyis. These compounds are of great interest due to their diverse. Enaminocarbonyl substrates with acrylate derivatives. Asymmetric synthesis, sulfinimine, nitrogen heterocycles contents 1. Nitrogencontaining heterocycles, organocatalysis, aminocatalysis, trienamine catalysis, activation mode, cycloaddition reactions. Mar 18, 2009 here, all aspects of the topic are presented in a compact manner.
Synthesis of nitrogen heterocycles using titanium isocyanate complex and. Such compounds serve as useful synthetic building blocks as the. Catalytic asymmetric synthesis of a nitrogen heterocycle through stereocontrolled direct photoreaction from electronically excited state. Buy asymmetric synthesis of nitrogen heterocycles on free shipping on qualified orders asymmetric synthesis of nitrogen heterocycles. Nitrogencontaining heterocycles nch, constitute an important group of molecules, which are widely extended in whole chemical space. The ee was determined by chiral highperformance liquid chromatography after oxidation to the alcohol. View the article pdf and any associated supplements and figures for a period of 48 hours. Importance of catalytic asymmetric synthesis of saturated. Asymmetric synthesis of heterocycles using sulfinimines n. Arylpyrrolidines and benzofused nitrogen heterocycles article pdf available in angewandte chemie international edition 5811 january 2019 with 60 reads.
Over the past 10 years, the wolfe group has developed efficient and highly diastereoselective pdcatalyzed carboamination reactions for the synthesis of pyrrolidines, ureas, pyrazolidines, isoxazolidines, morpholines and benzodiazepines in good. Ciamician, alma mater studiorum universita di bologna, via selmi 2, 40126 bologna, italy. Catalytic asymmetric synthesis of a nitrogen heterocycle. On the basis of this mechanism, it seemed reasonable to anticipate that the catalytic asymmetric synthesis of oxygen heterocycles might be achieved through the use of an appropriate chiral phosphine. Trienamines for the organocatalytic synthesis of nitrogen. The synthesis of nitrogen containing heterocycles is important due to the fact that many biologically active molecules contain these motifs. This is one property that many strategies in asymmetric synthesis have in common. Asymmetric synthesis of nitrogen heterocycles by reaction of. Later, sobota reported that the reaction of 1 with co 2 gave a titaniumisocyanate complex 2 eq. Recent advances in the application of ringclosing metathesis. A general, modular method for the catalytic asymmetric. Asymmetric synthesis of nitrogen heterocycles wiley online books. Asymmetric synthesis of biologically interesting heterocyclic compounds.
Synthesis of heterocycles using nitrogenationtransmetallation reaction. Meo o h n h n o o o o n ho aco meo o o o n ho oh azinomycin a azinomycin b n h n the antineoplastic activity of mitomycins a, b, and c 4, produced by strepto myces caespitosus, is associated with the high reactivity of the strained. Asymmetric synthesis of nitrogen heterocycles wiley online. Page 120 issue ichc20 arkivoc 2006 vii 120128 asymmetric synthesis of heterocycles using sulfinimines nsulfinyl imines franklin a. Apr 22, 2016 nitrogen bearing rings are very common features in the molecular structures of modern drugs. Despite the great progress, there are many unsatisfactory results in phosphinemediated asymmetric synthesis. Asymmetric synthesis of nitrogen heterocycles organic. The ring chain tautomerism of nitrogen heterocycles constitutes a fairly large area of organic chemistry. Many of the alkaloids contain complex polycyclic core. Mai a dissertation submitted in partial fulfillment of the requirements for the degree of doctor of philosophy chemistry in the university of michigan 2011 doctoral committee. Nevertheless, ring openingbased approaches to the synthesis of acyclic products are of obvious. A threestep tandem process for the synthesis of bicyclic. Synthesis of pyridines introduction intermediates used for the construction of aromatic heterocycles synthesis of aromatic heterocycles examples of commonly used strategies for heterocycle synthesis carbonheteroatom bond formation and choice of oxid ation state pyridines general properties, electronic structure. Scitech importance of catalytic asymmetric synthesis of.
Phosphinecatalyzed enantioselective synthesis of oxygen. For application to the asymmetric synthesis of nitrogen heterocycles, see. Pdf asymmetric synthesis of heterocycles using sulfinimines. Jie dai department of chemistry, room 18490, massachusetts institute of technology, cambridge, ma, 029 usa. The reactivity of photoexcited molecules has been extensively studied for decades but until today direct bondforming reactions of such excited. Chiral n,oheterocycles were synthesized in high yields and excellent enantioselectivity up to 97% ee via iridiumcatalysed intramolecular allylic substitution with nucleophilic attack by the amide oxygen atom. The synthesis of chiral nitrogencontaining saturated heterocycles has attracted the attention of organic chemists worldwide. Acycloaddition reaction products have also been extensively used in the synthesis of cyclic compounds through further transformations. Catalytic asymmetric addition of grignard reagents to alkenyl. Author links open overlay panel claude agami luc dechoux severine hebbe. Chiral semicorrins and related nitrogen heterocycles as. Advances in the organocatalytic asymmetric mannich. Useful intermediates for the stereoselective synthesis of nitrogen heterocycles and ligands for asymmetric catalysis andrea gualandi dipartimento di chimica g.
Phosphinemediated enantioselective synthesis of carbocycles. Asymmetric synthesis of mononitrogen heterocycles via the azamichael reaction. The important requirement for approval of a new drug, in case it happens to be chiral, that both enantiomers of the drug be studied in detail 1, have focused the attention of synthetic organic and medicinal chemists on the development of new methods for catalytic asymmetric synthesis especially of relevant saturated nheterocycles. A plausible pathway, originally suggested by trost, for the phosphinecatalyzed cyclization of hydroxy2alkynoates is illustrated in scheme 1.
Asymmetric synthesis of nitrogen heterocycles by jacques. Synthesis of unexpected nitrogen heterocycles via pd. Synthesis of nitrogen heterocycles using samariumii iodide. Using this procedure, various heterocycles, such as indole, quinoline, pyrrole, pyrrolizine, and indolizine derivatives, could be synthesized from molecular nitrogen in goodtomoderate yields as a stoichiometric reaction based on a titanium complex by a onepot reaction. Synthesis of chiral nitrogen heterocycles via the narasakaheck reaction we use cookies to ensure that our site works correctly and provides you with the best experience. Asymmetric synthesis of n,oheterocycles via enantioselective. Feringa chiral n,oheterocycles were synthesized in high yields and excellent enantioselectivity up to 97% ee via. Asymmetric palladiumcatalyzed reactions for the synthesis.
492 386 226 1554 583 1153 197 50 1233 716 1501 308 1093 343 398 1063 547 1422 981 999 408 896 707 762 497 805 776 513 312 275 1476