Divergent Pathways and Competitive Mechanisms of Metathesis Reactions between 3-Arylprop-2-ynyl Esters and Aldehydes: An Experimental and Theoretical Study

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F14%3A00431791" target="_blank" >RIV/61388963:_____/14:00431791 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1002/chem.201402551" target="_blank" >http://dx.doi.org/10.1002/chem.201402551</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201402551" target="_blank" >10.1002/chem.201402551</a>

Result language

angličtina

Original language name

Divergent Pathways and Competitive Mechanisms of Metathesis Reactions between 3-Arylprop-2-ynyl Esters and Aldehydes: An Experimental and Theoretical Study

Original language description

Mechanistic studies of the reaction between 3-arylprop-2-ynyl esters and aldehydes catalyzed by BF3Et2O were performed by isotopic labeling experiments and quantum chemical calculations. The reactions are shown to proceed by either a classical alkyne-carbonyl metathesis route or an unprecedented addition-rearrangement cascade. Depending on the structure of the starting materials and the reaction conditions, the products of these reactions can be Morita-Baylis-Hillman (MBH) adducts that are unavailable by traditional MBH reactions or E- and Z-alpha, beta-unsaturated ketones. O-18-Labeling studies suggested the existence of two different reaction pathways to the products. These pathways were further examined by quantum chemical calculations that employedthe DFT(wB97XD)/6-311+G(2d,p) method, together with the conductor-like screening model for realistic solvation (COSMO-RS). By using the wB97XD functional, the accuracy of the computed data is estimated to be 1-2kcalmol(-1), shown by the

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

<a href="/en/project/GA14-31419S" target="_blank" >GA14-31419S: Computational Design of Minimalistic Metallopeptides: ‘En Route’ to Disentangling the Catalytic Power of Metalloproteins</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2014

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Volume of the periodical

20

Issue of the periodical within the volume

33

Country of publishing house

DE - GERMANY

Number of pages

11

Pages from-to

10360-10370

UT code for WoS article

000340469800026

EID of the result in the Scopus database

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