Unusual H/D isotope effect in isomerization and keto–enol tautomerism reactions of pyruvic acid: nuclear quantum effect restricts some rotational isomerization reactions
نویسندگان
چکیده
منابع مشابه
A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.
While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve ...
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A new coupling-isomerization-Claisen domino reaction starting from electron deficient halides and 1-(hetero)aryl propargyl trityl ethers dichotomizes in the concluding steps of the sequence and gives rise to the formation of tricyclo[3.2.1.0(2,7)]oct-3-enes, enones, 1H-isochromenes, or indans as a consequence of minute differences of substituent effects.
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The mechanisms of the photochemical isomerization reactions were investigated theoretically using a model system of 2-cyanopyrrole and 2-cyano-5-methylpyrrole with the CASSCF (eight-electron/seven-orbital active space) and MP2-CAS methods and the 6-311(d,p) basis set. The structures of the conical intersections, which play a decisive role in such phototranspositions, were obtained. The intermed...
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ژورنال
عنوان ژورنال: RSC Advances
سال: 2017
ISSN: 2046-2069
DOI: 10.1039/c6ra28271g