scholarly journals Spiro[1,2]oxaphosphetanes of Nonstabilized and Semistabilized Phosphorus Ylide Derivatives: Synthesis and Kinetic and Computational Study of Their Thermolysis

2020 ◽  
Vol 85 (22) ◽  
pp. 14570-14591
Author(s):  
Jesús García López ◽  
Pablo M. Sansores Peraza ◽  
María José Iglesias ◽  
Laura Roces ◽  
Santiago García-Granda ◽  
...  
Keyword(s):  
Computational Study ◽  
Phosphorus Ylide

Computational study on the mechanism of the three-component reaction of dimethylacetylene dicarboxylate and triphenylphosphine with 2-acetylbutyrolactone

2015 ◽  
Vol 93 (6) ◽  
pp. 666-672 ◽  
Author(s):  
Mina Haghdadi ◽  
Sakineh Asghari ◽  
Samaneh Ramezani
Keyword(s):  
Density Functional ◽  
Wittig Reaction ◽  
Computational Study ◽  
Density Functional Theory Method ◽  
Functional Theory ◽  
Phosphorus Ylide ◽  
Intramolecular Wittig Reaction ◽  
Ring Opening Reaction ◽  
The Density Functional Theory ◽  
Three Component Reaction

The molecular mechanism of the three-component reaction of triphenylphosphine, dialkyl acetylene dicarboxylate, and 2-acetylbutyrolactone to synthesize the stabilized phosphorus ylide and 1,3-butadiene derivative via the intramolecular Wittig reaction has been investigated using the density functional theory method at the B3LYP/6-31G level of theory. Two possible reaction pathways have been characterized in detail to form the cyclobutene intermediate and in the next step; the cyclobutene intermediate undergoes the conrotatory ring-opening reaction to produce the 1,3-butadiene derivative along two possible pathways. The calculated results indicate that two pathways (pathways II and II-a) are the most energy favorable among all of the pathways, so they occur more than do the others. Moreover, the phosphorus ylide is more stable than the corresponding 1,3-butadiene, demonstrating that the intramolecular Wittig reaction could not easily occur at room temperature, which is in agreement with the experimental results.

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