NDLI: Mechanistic investigations into the cyclopropanation of electron-deficient alkenes with ethyl diazoacetate using [Co(MeTAA)]

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Mechanistic investigations into the cyclopropanation of electron-deficient alkenes with ethyl diazoacetate using [Co(MeTAA)]

Content Provider	Semantic Scholar
Author	Chirila, Andrei Brands, Maria B. Bruin, Bas De
Copyright Year	2018
Abstract	Abstract A detailed mechanistic study of the cyclopropanation of electron-deficient alkenes, namely methyl acrylate with ethyl diazoacetate (EDA), was carried out, aiming at understanding both the superior activity and the higher sensitivity of the cobalt(II) tetramethyldibenzotetraaza[14]annulene [Co(MeTAA)] catalyst as compared with cobalt(II) tetraphenylporphyrin [Co(TPP)]. Cobalt(III)-carbene radicals were demonstrated to be present as key intermediates in the reaction, using a combination of kinetic studies, experimental EPR spin-trapping experiments, and supporting DFT studies. Reaction progress was monitored in real time by observing N 2 formation and measuring its partial pressure under isothermal conditions. Reaction progress kinetic analysis (RPKA) was used to analyze the experimental data. Results showed that the reaction is first-order in both [catalyst] and [EDA] and zero-order in [methyl acrylate], in agreement with the DFT-calculated mechanism. The calculated activation parameters corresponding to the rate-determining step of the reaction are in agreement with the experimental values, thus providing strong support for the proposed metalloradical mechanism.
Starting Page	347
Ending Page	360
Page Count	14
File Format	PDF HTM / HTML
DOI	10.1016/j.jcat.2018.02.013
Alternate Webpage(s)	https://pure.uva.nl/ws/files/18213088/Chapter_3.pdf
Alternate Webpage(s)	https://pure.uva.nl/ws/files/32224510/Chirila_JCatal_2018.pdf
Alternate Webpage(s)	https://doi.org/10.1016/j.jcat.2018.02.013
Volume Number	361
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article

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