Matches in SemOpenAlex for { <https://semopenalex.org/work/W4385576237> ?p ?o ?g. }
- W4385576237 endingPage "11967" @default.
- W4385576237 startingPage "11954" @default.
- W4385576237 abstract "The kinetic data indicate that the addition of tertiary phosphines to α-methylene lactones in acetic acid is strongly accelerated in comparison to the reactions of related open-chain esters. Six-membered α-methylene-δ-valerolactone exhibited a more pronounced rate increase than five-membered α-methylene-γ-butyrolactone. The use of α-methylene-γ-butyrolactam as a nitrogen analogue of α-methylene-γ-butyrolactone resulted in a total loss of the reaction acceleration. The observed reactivities were rationalized by DFT calculations at the RwB97XD/6-31+G(d,p) level of theory, showing that the intramolecular interaction between phosphonium and enolate oxygen centers provided by the locked s-cis-geometry of the heterocycles plays an important role in the stabilization of intermediate zwitterions. The reactivity is also controlled by the conformational flexibility of the heterocycle. The geometries of five-membered and, especially, six-membered lactone cycles are slightly changed upon the nucleophilic attack of phosphine, leading to the stabilizing stereoelectronic effect by the Ρ···Ο interaction. The addition of phosphine to α-methylene-γ-butyrolactam significantly distorts the initial geometry of the heterocycle, making the nucleophilic attack unfavorable. The application of the stereoelectronic effect to enhance the efficiency of the phosphine-catalyzed Michael and Pudovik reactions of α-methylene lactones was demonstrated." @default.
- W4385576237 created "2023-08-05" @default.
- W4385576237 creator A5002872807 @default.
- W4385576237 creator A5016339316 @default.
- W4385576237 creator A5048762665 @default.
- W4385576237 creator A5056173281 @default.
- W4385576237 creator A5091636547 @default.
- W4385576237 date "2023-08-04" @default.
- W4385576237 modified "2023-09-27" @default.
- W4385576237 title "Stereoelectronic Effect in the Reaction of α-Methylene Lactones with Tertiary Phosphines and Its Application in Organocatalysis" @default.
- W4385576237 cites W1228178927 @default.
- W4385576237 cites W1587208382 @default.
- W4385576237 cites W1801794661 @default.
- W4385576237 cites W1965525266 @default.
- W4385576237 cites W1974208904 @default.
- W4385576237 cites W1976406005 @default.
- W4385576237 cites W1980992485 @default.
- W4385576237 cites W1982885168 @default.
- W4385576237 cites W1983292760 @default.
- W4385576237 cites W1989109779 @default.
- W4385576237 cites W1991520288 @default.
- W4385576237 cites W1995995998 @default.
- W4385576237 cites W1997445806 @default.
- W4385576237 cites W2004006678 @default.
- W4385576237 cites W2011141497 @default.
- W4385576237 cites W2011529244 @default.
- W4385576237 cites W2020086312 @default.
- W4385576237 cites W2020165342 @default.
- W4385576237 cites W2027314483 @default.
- W4385576237 cites W2030841140 @default.
- W4385576237 cites W2035340879 @default.
- W4385576237 cites W2035773881 @default.
- W4385576237 cites W2037451324 @default.
- W4385576237 cites W2037740612 @default.
- W4385576237 cites W2041726370 @default.
- W4385576237 cites W2044429383 @default.
- W4385576237 cites W2050429240 @default.
- W4385576237 cites W2056809800 @default.
- W4385576237 cites W2057228513 @default.
- W4385576237 cites W2061698805 @default.
- W4385576237 cites W2063371414 @default.
- W4385576237 cites W2066103357 @default.
- W4385576237 cites W2067260879 @default.
- W4385576237 cites W2068871883 @default.
- W4385576237 cites W2073887717 @default.
- W4385576237 cites W2079842424 @default.
- W4385576237 cites W2081863961 @default.
- W4385576237 cites W2093800776 @default.
- W4385576237 cites W2102238139 @default.
- W4385576237 cites W2105011549 @default.
- W4385576237 cites W2112409250 @default.
- W4385576237 cites W2116005630 @default.
- W4385576237 cites W2117133936 @default.
- W4385576237 cites W2143945519 @default.
- W4385576237 cites W2147604989 @default.
- W4385576237 cites W2150661208 @default.
- W4385576237 cites W2154594399 @default.
- W4385576237 cites W2168198108 @default.
- W4385576237 cites W2221684297 @default.
- W4385576237 cites W2327978817 @default.
- W4385576237 cites W2343313833 @default.
- W4385576237 cites W2396980957 @default.
- W4385576237 cites W2418389840 @default.
- W4385576237 cites W2508343881 @default.
- W4385576237 cites W2564708666 @default.
- W4385576237 cites W2589944273 @default.
- W4385576237 cites W2604300844 @default.
- W4385576237 cites W2606644996 @default.
- W4385576237 cites W2611457683 @default.
- W4385576237 cites W2619447959 @default.
- W4385576237 cites W2752574824 @default.
- W4385576237 cites W2754093761 @default.
- W4385576237 cites W2754447875 @default.
- W4385576237 cites W2765618240 @default.
- W4385576237 cites W2900893139 @default.
- W4385576237 cites W2916801576 @default.
- W4385576237 cites W2949884981 @default.
- W4385576237 cites W2951173094 @default.
- W4385576237 cites W2951591712 @default.
- W4385576237 cites W2952211134 @default.
- W4385576237 cites W2952560816 @default.
- W4385576237 cites W2954037484 @default.
- W4385576237 cites W2955144486 @default.
- W4385576237 cites W2955256592 @default.
- W4385576237 cites W2957443520 @default.
- W4385576237 cites W2963686657 @default.
- W4385576237 cites W2976807707 @default.
- W4385576237 cites W2990846635 @default.
- W4385576237 cites W2995503488 @default.
- W4385576237 cites W3004070227 @default.
- W4385576237 cites W3008456148 @default.
- W4385576237 cites W3008692840 @default.
- W4385576237 cites W3028226744 @default.
- W4385576237 cites W3046187855 @default.
- W4385576237 cites W3048367773 @default.
- W4385576237 cites W3048425538 @default.
- W4385576237 cites W3096856005 @default.
- W4385576237 cites W3107783814 @default.