Ylide compounds heterocyclic synthesis

Cascade reactions of carbonyl ylides for heterocyclic synthesis 09PHC20. Citronellal as key compound in organic synthesis, particularly, of heterocycles 07T6671. 

Tandem carbonyl ylide generation from the reaction of metallo carbenoids with carbonyl continues to be of great interest both mechanistically and synthetically. Effective carbonyl ylide formation in transition metal catalyzed reactions of diazo compounds depends on the catalyst, the diazo species, the nature of the interacting carbonyl group and competition with other processes. The many structurally diverse and highly successful examples of tetrahydrofuran formation cited in this mini-review clearly indicate that the tandem cyclization/cycloaddition cascade of metallo carbenoids has evolved as an important strategy in both carbo- and heterocyclic synthesis. 

Heterocyclic Synthesis. - The reactions of phosphorus ylides with phenan-threne-9,10-quinone (113) have been used to prepare phenanthrene [9,10-x]-fused compounds with four, five, and six membered heterocyclic rings. (E)-4-carbethoxymethylene-l,2,3,4-tetrahydro-2-quinolones 114 have been obtained from the stereoselective reaction of 3-hydroxy-1,2,3,4-tetrahydroquinoline-2,4-diones and ethyl(triphenylphosphoranylidene)acetate. A -trifluoroacetylanilines 115 react with Ph3P=C02Et producing enamine derivatives 116 as a mixture of (E)- and (Z)-isomers. Enamines 116 are useful precursors for the synthesis of indoles and quinolones. 

Figure 9 intramolecular ylide formation by rhodium catalyzed decomposition of diazo compounds application to heterocycle synthesis. 

The 1,3-dipolar cycloaddition reactions to unsaturated carbon-carbon bonds have been known for quite some time and have become an important part of strategies for organic synthesis of many compounds (Smith and March, 2007). The 1,3-dipolar compounds that participate in this reaction include many of those that can be drawn having charged resonance hybrid structures, such as azides, diazoalkanes, nitriles, azomethine ylides, and aziridines, among others. The heterocyclic ring structures formed as the result of this reaction typically are triazoline, triazole, or pyrrolidine derivatives. In all cases, the product is a 5-membered heterocycle that contains components of both reactants and occurs with a reduction in the total bond unsaturation. In addition, this type of cycloaddition reaction can be done using carbon-carbon double bonds or triple bonds (alkynes). 

Heterocycles.—The phosphonium salt (59) is an effective three-carbon synthon, as demonstrated by its reaction with enolates of /9-keto-esters (Scheme 20) to give cyclopentenyl sulphides via an intramolecular Wittig reaction.63 Ylides are also intermediates in the synthesis of dihydrofurans (60) from the cyclopropylphos-phonium salt (61) and sodium carboxylates (Scheme 21).64 Cumulated ylides are very useful for the synthesis of heterocyclic compounds, e.g. (62), from molecules which contain both an acidic Y—H bond and a carbonyl or nitroso-function, as shown in Scheme 22.65... 

In comparison with other 1,3-dipoles that have been extensively explored in organic synthesis (7), sulfur-centered 1,3-dipoles (1-4) are rather uncommon species. However, within the last two decades, remarkable progress has been made regarding both methods of generation and synthetic applications. In particular, thiocarbonyl ylides (1) were established as key intermediates useful for the preparation of sulfur-containing heterocyclic compounds. General methods for the preparation of thiocarbonyl ylides and their chemical reactivity have been reviewed (8-11). 

Reaction of Azolium Ylides with Dialkyl Acylphosphonate New Synthesis of Heterocyclic Compounds A. Takamizawa et al., Heterocycles, 1974, 2, 521-554. 

Ring synthesis from non-heterocycles by closure y to the heteroatom are reported. Sulfonium ylides (135) with active methylene compounds such as malononitrile give a C-phenacyl product (136) however, when reacted with /3-diketones and /3-ketonic esters they produce furans quantitatively (74CL101). In these cases O-phenacylation takes place followed by cyclization to give the 3-hydroxydihydrofuran (137), which is dehydrated to the furan (138) (Scheme 30). These furans differ from those formed by the reaction of the diketone or ketonic esters with phenacyl halides. The latter reaction takes place by C-phenacylation, yielding the isomeric furans (139). 

The generation and reactivity of conjugated azomethine ylides has been reviewed.148 1,3-Dipolar cycloaddition and 1,5- and 1,7-electrocyclizations have been described as powerful strategies for the synthesis of monocyclic and annulated five- and seven-membered nitrogen heterocyclic compounds. 

Lothar Weber was born in 1944 in Langenols in Schlesien. He studied at the Universitat Marburg and received his doctorate there under the direction of Professor Gunter Schmid in 1973. Thereafter he carried out postdoctoral studies with Professor Barry M. Trost at the University of Wisconsin in Madison, USA. On his return to Marburg, he began the experimental work leading to his habilitation, which was completed in 1982 at the Universitat Essen. His work focused on the coordination chemistry of sulfur ylides. In 1985, he became a C2 Professor and then joined the Fakultat fiir Chemie der Universitat Bielefeld. His research interests include the chemistry of compounds with low-coordinate elements of the fifth main group, the synthesis of homo- and heterocycles with heavy elements, as well as new aspects in boron chemistry. 

The publications that appeared up to 1975 on the transformations of oxiranes into other heterocyclic compounds are reviewed in detail in the monograph by van der Plas and the relevant chapters of other reviews. Accordingly, we merely supplement the earlier data with more recently reported results and, at the same time, present some of the varied transformations of the oxiranes. The possibility of stereoselective synthesis of heterocyclic systems was broadened considerably by 1,3-dipolar cycloaddition reactions. Heterocycles are formed if the ylide intermediates produced from oxiranes in photolytically or thermally induced reactions are made to react intramolecularly or with external dipolarophiles. Reactions of these types will be treated in Sections IV.8 and IV.9. 

The reactions between triphenylphosphine and acetylenic esters have been used to produce a number of different ylidic species including (31), dialkyl 2-(imido-iV-yl)-3-(triphenylphosphoranylidene)butanedioates (32), the steri-cally congested ylide (33) and heterocyclic phosphonium ylides (34). Thiazolyl derivatives, such as (35) and (36) have also been prepared and utilised in the synthesis of heterocylic compounds ... 

The [2 + 2] cycloaddition and the [4 + 2] addition of vinylidenephosphorane with heteroallenes have been applied to the synthesis of a great variety of four- and six-membered heterocyclic compounds carrying an exocyclic ylide function. - ... 

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