The reaction of trimethylsilyl-substituted sulfonium ylides with organoboranes (Ph(3)B, Et(3)B) has been studied and although homologated products were obtained in good yield (after oxidation to the corresponding alcohols), the enantiomeric excesses were low with our camphor-based chiral sulfide (up to 40% ee, cf. corresponding phenyl-substituted sulfonium ylides gave >95% ee). Cross-over exper...

Cycloaddition reactions are among the most powerful methods for the synthesis of complex compounds. 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 five-membered heterocycles. Azomethine ylides are commonly used as dipoles for the synthesis of...

A new ylide-initiated tandem cyclization reaction based on γ-dialkylation of allylic ylides has been realized, delivering a series of [3.3.0] oxa-bicyclic dienes in high yields with perfect diastereoselectivity.

New oligomers or polymers are prepared by polymerization of arsonium ylides in the presence of boron compounds.

Merophosphinine and phosphinine dyes were reported as phosphorus atom equivalents of merocyanine cyanine in the 1960s. Although these are excellent sensitizers for enhancing photographic performance, their development has been considerably retarded because difficulties synthetic process. Previously, while investigating reactivity fluoroalkenes with various nucleophiles, we developed fluorinated...

The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c ...

A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(ii) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic...

The use of ylides of P, N, As or S as ligands toward transition metals is still a very active research area in organometallic chemistry. This fact is mainly due to the nucleophilic character of the ylides and to their particular bonding properties and coordination modes. They can behave as monodentate or bidentate –chelate or bridging– species, they can be used as chiral auxiliary reagents, the...

The one-carbon ring expansion of 1-deoxy-1-thio-1,6-anhydrosugars, mediated by metal carbenes and proceeding through the intermediacy of sulfur ylides, has been proposed as a route for the synthesis of the tagetitoxin skeleton. Intermolecular reactions of such thioanhydrosugars with diazoesters afford a range of undesired products derived from the initially formed ylide, whereas use of an intra...