The cis-trans ratio of the alkenes formed in Wittig reactions of semistabilised ylides (derived from benzyltriarylphosphonium salts in ethanolic sodium ethoxide) with benzaldehyde, acetaldehyde or trimethylacetaldehyde increases as steric crowding at phosphorus increases. In contrast, the cis-trans ratio of the unsaturated esters formed in the related reactions of the stabilised ethoxycarbonylm...

Pseudo-C2-symmetric chiral phosphorus ylides have been designed and synthesized for the enantioselective preparation of allenic esters, and up to 92% ee has been achieved.

The reaction o f 1-hydroxyxanthenone (1) and hydroxyquinoline (10, 13) Mannich bases with the reactive phosphacumulated ylides (2), represents a new way for the synthesis o f the pyranones and pyranthiones (5, 11, 14). On the other hand, the stabilized phosphorus ylides (6) affect the transylidation o f the Mannich base (1) to the corresponding phosphoranylidenes (9). The structure o f the resu...

BACKGROUND Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes ...

We describe the nearly quantitative preparation of phosphorus ylides and the Wittig reaction occurring in the solid sate during high-energy mechanochemical processing. Initial insights into the details of the discovered chemical transformations indicate that high-energy mechanical processing supports the interaction of reacting centers by breaking crystallinity of the reactants and by providing...

Preparation of new types of trisubstituted oxazoles is realized via chemoselective O-acylations and intramolecular Wittig reactions with ester functionalities using in situ formed phosphorus ylides as key intermediates. A plausible reaction mechanism for this undiscovered chemistry is also proposed based on the existence of expected and rearranged isomeric oxazoles.

Phosphine-catalyzed [4+1] annulation of electron-deficient 1,3-dienes or 1,3-azadienes with maleimides has been successfully developed under very mild conditions, providing a convenient and highly efficient method for constructing 2-azaspiro[4.4]nonenes and 1,7-diazaspiro[4.4]nonenes. This reaction represents the first example of [4+1] cyclization between electron-deficient 4π-conjugated system...