kinetic studies were made of the reactions between triphenylphosphine 1, dialkyl acetylenedicarboxylates 2 in the presence of nh-acid, such as maleimid (as a protic/nucleophilic reagent) 3. to determine the kinetic parameters of the reactions, they were monitored by uv spectrophotometery. the second order fits were automatically drawn and the values of the second order rate constant (k2) were a...

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 ...

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...

Stable crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reactionbetween hydantoins or thiohydantoins and dialkyl acetylenedicarboxylates in the presence oftriphenylphosphine. These phosphoranes undergo smooth intramolecular Wittig reaction followedby an electrocyclic ring opening to produce dialkyl (E)-2-(2,5-dihydro-5,5-diaryl-2-thioxo-1H-imidazol-4-yl)fum...

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.

stable crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reactionbetween hydantoins or thiohydantoins and dialkyl acetylenedicarboxylates in the presence oftriphenylphosphine. these phosphoranes undergo smooth intramolecular wittig reaction followedby an electrocyclic ring opening to produce dialkyl (e)-2-(2,5-dihydro-5,5-diaryl-2-thioxo-1h-imidazol-4-yl)fum...