Intramolecular cycloadditions of X=Y-ZH systems.

by Maurice William Jordan

Written in English
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Thesis (Ph. D.)--The Queen"s University of Belfast, 1982.

The Physical Object
Pagination1 v
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Open LibraryOL19980220M

Highly efficient and atom economic synthesis such as one-pot reactions and multicomponent reactions (MCRs) have gained increasing popularity in the synthesizing of complex molecules including triazolobenzodiazepine-type compounds [10,11,12,13,14,15].For example, the Martin group reported a cascade reductive amination and intramolecular [3 + 2] cycloaddition reaction sequence for triazole .   We also explored intramolecular [2+2] cycloadditions of 2-acylimidazoles. In these experiments, we observed somewhat higher yields when the loading of LiBF 4 was reduced to equiv. These conditions enabled intramolecular cycloadditions with a variety of acceptor moieties, including esters, ketones, and amides (Figure 2, 12–15).The use of an α-substituted Michael acceptor required. The utility of 2-isoxazolines (Δ 2-isoxazolines, 4,5-dihydroisoxazoles) in the preparation of natural products and other compounds of medicinal and materials interest is growing because the 2-isoxazoline serves both as a desirable functional group and a versatile synthetic e oxide cycloaddition (NOC) to alkenes is the most common method for the preparation of 2. Ma, B.; Snyder, J. K. “Development of a New Cobalt Catalyst System for the [4 + 2 + 2] Cycloadditions of Functionalized Norbornadienes and Butadiene.” Organometallics , 21, -

  Mejia-Oneto JM, Padwa A () Intramolecular [3+2]-cycloaddition reaction of push-pull dipoles across heteroaromatic p-systems. Org Lett – CrossRef Google Scholar Scheme 2. Formal [3+2] cycloadditions via aziridinium ions. enes, alkynes, ketones, aldehydes, nitriles, and heterocumul-enes to afford formal 1,3-dipolar cycloadducts.[2] It has also been reported that the nonactivated aziridine 4 (Scheme 2) reacts with acetylenecarboxylates to afford di-polar intermediates 5, followed by intramolecular attack of.   Thiophene S-oxides constitute a class of molecules that have been studied in more detail only recently. Their existence as intermediates in the peracid mediated oxidation of thiophenes to thiophene S,S-dioxides, however, has been known over some time. Over the last 20 years, a larger number of thiophene S-oxides have been prepared and isolated in pure form. and Vinyl Sulfide Systems", I. Ojima and K. Kondo, Bull. Chem. Soc. Japan, 46, l (l). "Reactions of Diphenylphosphinothioyl Isothiocyanate and Related Compounds with Some Nucleophiles and.

  Ranging from hydrogenation to hydroamination, cycloadditions and nanoparticles, this first handbook to comprehensively cover the topic of iridium in synthesis discusses the important advances in iridium-catalyzed reactions, namely the use of iridium complexes in enantioselective catalysis. A must for organic, complex and catalytic chemists, as well as those working with/on . V. Cationic [2 + 2] Cycloadditions We have been developing thermally driven [2 + 2] cycloadditions for constructing cyclobutanes, which is an effort that will contribute significantly to an area of cycloaddition chemistry that is under-explored. A successful cationic version of [2 + 2] cycloaddition would also represent a bio-mimetic process to. Vinyl Sulfide Systems", I. Ojima and K. Kondo, Bull. Chem. Soc. Japan, 46, l (l). "Reactions of Diphenylphosphinothioyl Isothiocyanate and Related Compounds with Some Nucleophiles and. "In vitro and in vivo cancer cell apoptosis triggered by competitive binding of Cinchona alkaloids to the RING domain of TRAF6."Qi,Y.; Zhao, X.; Chen, J.

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Intramolecular cycloadditions of X=Y-ZH systems Author: Jordan, M. ISNI: Awarding Body: Queen's University of Belfast Current Institution: Queen's University Belfast Date of Award: Availability of Full Text: Full text unavailable from EThOS.

Intramolecular cycloadditions of nitrones are especially useful in synthesis. 40,41 The alkenylnitrone is generated by the condensation of (E)heptenal with N-methylhydroxylamine, which undergoes intramolecular cycloaddition to give a cis bicyclic isoxazolidine (Fig. Type II intramolecular cycloadditions ([4+2], [4+3], [4+4] and [5+2]) have emerged recently as an efficient and powerful strategy for the construction of bridged ring systems.

In general, type II cycloadditions provide access to a wide range of bridged bicyclo[m.n.1] ring systems with high regio. Group Meeting O'Malley Higher Order Cycloadditions in Synthesis 8/30/ 4 [6 + 2] Cycloadditions Feldman has studied the photochemical intramolecular cycloadditions of tropones.

(JOC,54(3), ).This reaction was applied in a synthesis of (+)-dactylol. As the π-systems are not conjugated these reactions were treated as cycloadditions. Figure S3. Photochemical conversion of ciromycin A to ciromycin B2 Figure S4. Reported structures of ML and BE;4 the C6-C7 olefin (highlighted in red) is a trans-double bond.

The first intramolecular (4+3) cycloaddition of pyrroles with epoxy enolsilanes as the electrophiles was developed and used to generate optically‐enriched cycloadducts.

A type II intramolecular oxidopyrylium‐mediated [5+2] Intramolecular cycloadditions of X=Y-ZH systems. book reaction allows the efficient and diastereoselective formation of various highly functionalized and synthetically challenging bridged seven‐membered ring systems (such as bicyclo[]undecane, bicyclo[]decane, bicyclo[]dodecane, and bicyclo[]]tridecane).

A series of intramolecular cycloaddition reactions were then attempted on mono- and tris-2H-chromenes. It was found that intramolecular [2+2] cycloadditions proceeded adequately, however, intramolecular [2+4] cycloadditions were unsuccessful.

Thus, preliminary investigations were then undertaken towards the synthesis of functionalized. Alkynes in Cycloadditions presents a comprehensive summary of the literature on methods for the synthesis of ring systems from acetylenes for academic researchers working in the fields of organic synthesis, physical organic chemistry, organometallic chemistry, catalysis, materials science, nanomaterials and biochemistry.

Book Chapters Year Publication ; 'X:Y- ZH systems as potential 1, 3- dipoles. Part Discussion of Efficient, microwave-assisted intramolecular 1,3-dipolar cycloadditions of oximes and N-methylnitrones derived from o-alkenylmethoxyacetophenones. Heaney, F. Cycloaddition reactions, in general, are one of the most powerful and frequently applied methods for the construction of cyclic frameworks.

1 In general, [m+n] cycloadditions can be induced by heat, light, Lewis acids, high pressure, and sonication. 1 The [2+2] cycloaddition is a thermally forbidden process as predicted by the Woodward–Hoffmann rules, 2 but it can be achieved photochemically. Corresponding intramolecular 1,3-dipolar cycloadditions of N-methylnitrones (B), generated in situ from o-alkenylmethoxy-acetophenones (1a–1c) and N-methylhydroxylamine under solvent-free microwave irradiation conditions, are completely regio- and stereoselective, require much shorter reaction times, and afford adducts (4a–4c) in higher.

Synchronous intramolecular cycloadditions of the polyene macrolactam polyketide heronamide C. Authors: Booth, Thomas J and Alt, Silke and Capon, Robert J and Wilkinson, Barrie A growing number of natural products appear to arise from biosynthetic pathways that involve pericyclic reactions.

Abstract. Treatment of allenyl tosyl hydrazones 10a,b with BuLi in THF at 0°C, with subsequent reflux for 2 hrs, resulted in the exclusive formation of 4,4-dimethy alky1idenediazabicyclo[hexenes 12a,b, in high gh rather unstable at room temperature, the formation of these products represent the first observation of a formal nitrene-type 1,1-cycloaddition of an.

Title: Recent Advances in Intramolecular Nitrile Oxide Cycloadditions in the Synthesis of 2-Isoxazolines VOLUME: 8 ISSUE: 5 Author(s):Cindy C. Browder Affiliation:Department of Chemistry and Biochemistry, Northern Arizona University, PO BoxFlagstaff, AZ USA.

Keywords:Asymmetric reaction, Intramolecular nitrile oxide cycloaddition, Intramolecular 1,3-dipolar. The intramolecular [4 + 2] cycloaddition reactions of c,-alkynyl carbonyl compounds are described. This reaction, the first heterocyclic variant of the enyne cycloaddition reaction, affords a product with a dihydroisobenzofuran ring system.

We have been embarking on the chemistry of allenamides in the last ten years. 1, 2 In particular, allenamides have proven to be an excellent source of nitrogen-stabilized oxyallyl cations 3, 4 through DMDO-epoxidation, thereby allowing us to develop highly stereoselective [4 + 3] cycloaddition manifolds 5 – 7 including intramolecular 8, 9 cycloadditions such as using N-tethered allenamide 1.

The first experimental examples of Diels–Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the MX functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model.

The 1,3. Chemically Induced Anion Radical Cycloadditions: Intramolecular Cyclobutanation of Bis(enones) via Homogeneous Electron Transfer. Journal of the American Chemical Society(6), Finally, several applications of intramolecular ortho-quinodimethane cycloadditions for the synthesis of natural products are described.

Introduction 2. Intramolecular Thermal Additions of Benzocyclobutenes Olefinic and Acetylenic Systems as Dienophiles Carbonyl, Imino, and Nitrile Systems as Dienophiles Synthesis of spiro[bicyclo[]heptane-2,2'-furan]amines via stereoselective cycloadditions of trimethylenemethane to (1S,3EZ,4R)arylimino-1,7,7-trimethylbicyclo[]heptanones.

5-Heterosubstituted 4-methylene-4,5-dihydroisoxazoles: Ready accessibility and versatile reactivity. Broggini, C. Larosa, G.

Zecchi, Synlett,Key Words. Causation in a Cascade: The Origins of Selectivities in Intramolecular Nitrone Cycloadditions. Elizabeth H Krenske, Sesil Agopcan, Viktorya Ayiyente, KN Houk, Brian A Johnson, Andrew B Holmes X=y-Zh Systems Oximes Hartree-Fock Density Functionals.

Title:Intramolecular Pauson-Khand Reaction of Alkyne-Ketenimines and Related [4+2] and [2+2] Cycloadditions VOLUME: 15 ISSUE: 5 Author(s):Mateo Alajarin*, Francisco-Jose Ballester and Angel Vidal* Affiliation:Departamento de Quimica Organica, Facultad de Quimica, Universidad de Murcia, Regional Campus of International Excellence "Campus Mare Nostrum", Espinardo, Murcia.

The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine- triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs), pyrrolo[1,2,5]benzothiadiazepines (PBTDs), and azetidino[1,4]benzodiazepines.

Solvent-free intramolecular 1,3-dipolar cycloadditions initiated by microwaves: Autoři: POSPÍŠIL, Jiří ( Česko) a Milan POTÁČEK ( Česko, garant). Vydání: 1. vyd. Spa, Book of abstracts, 6th Sigma-Aldrich Organic Synthesis Meeting, s.

Nakladatel: Sigma-Aldrich. A [4+3] cycloaddition is a cycloaddition between a four-atom π-system and a three-atom π-system to form a seven-membered ring. Allyl or oxyallyl cations (propenyliumolate) are commonly used three-atom π-systems, while a diene (such as butadiene) plays the role of the four-atom represents one of the relatively few synthetic methods available to form seven-membered rings.

Au catalyzed enatioselective intramolecular [4+3] cycloadditions of allene-dienes Fernando lopez etc, Angew. Chem. Int. Ed,50, Au catalyzed [4+3] cycloadditions in natural product synthesis Benjamin W.

Gung etc, chem. Eur.16, Alkynes in Cycloadditions presents a modern review of regioselective synthesis of aromatic and non-aromatic carbocyclic and heterocyclic ring systems based primarily on [2+2+2] and [4+2] cycloadditions, and other reactions of acetylenic units including enediynes and enyne-allenes.

Richard P. Hsung's research works w citations and 3, reads, including: In vitro and in vivo cancer cell apoptosis triggered by competitive binding of Cinchona alkaloids to the.

Cycloadditions affording bicyclo[n] systems and bridged-ring adducts from cyclic dienes conclude this survey which is followed by a discussion of unreactive trienes and a brief analysis of synthetic strategy to complete the review.- specialised degradation chemistry books Intramolecular cycloadditions.

h. Zeneth is an expert knowledge-based system for the prediction of forced degradation Helps understand mechanistic pathways as well as aid degradant identification and structure elucidation.Intramolecular reactions, especially ones leading to the formation of 5- and 6-membered rings, are rapid compared to an analogous intermolecular process.

This is largely a consequence of the reduced entropic cost for reaching the transition state of ring formation and the absence of significant strain associated with formation of rings of these.