Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/101704
Type: Artigo de periódico
Title: Mono And Double Polar [4 + 2+] Diels-alder Cycloaddition Of Acylium Ions With O-heterodienes
Author: Meurer E.C.
Eberlin M.N.
Abstract: Gas-phase reactions of acylium ions with α, β-unsaturated carbonyl compounds were investigated using pentaquadrupole multiple-stage mass spectrometry. With acrolein and metacrolein, CH3-C+=O, CH2=CH-C+=O, C6H5-C+=O, and (CH3)2N-C+=O react to variable extents by mono and double polar [4 + 2+] Diels-Alder cycloaddition. With ethyl vinyl ketone, CH3-C+=O reacts exclusively by proton transfer and C6H5-C+=O forms only the mono cycloadduct whereas CH2=CH-C+=O and (CH3)2N-C+=O reacts to great extents by mono and double cycloaddition. The positively charged acylium ions are activated O-heterodienophiles, and mono cycloaddition occurs readily across their C+=O bonds to form resonance-stabilized 1,3-dioxinylium ions which, upon collisional activation, dissociate predominantly by retro-addition. The mono cycloadducts are also dienophiles activated by resonance-stabilized and chemically inert 1,3-dioxonium ion groups, hence they undergo a second cycloaddition across their polarized C=C ring double bonds. 18O labeling and characteristic dissociations displayed by the double cycloadducts indicate the site and regioselectivity of double cycloaddition, which are corroborated by Becke3LYP/6-311++G(d,p) calculations. Most double cycloadducts dissociate by the loss of a RCO2COR1 molecule and by a pathway that reforms the acylium ion directly. The double cycloadduct of the thioacylium ion (CH3)2N-C+=S with acrolein dissociates to (CH3)2N-C+=O in a sulfur-by-oxygen replacement process intermediated by the cyclic monoadduct. The double by cycloaddition can be viewed as a charge-remote type of polar [4 + 2+] Diels-Alder cycloaddition reaction. Copyright © 2001 John Wiley & Sons, Ltd.
Editor: 
Rights: fechado
Identifier DOI: 10.1002/jms.267
Address: http://www.scopus.com/inward/record.url?eid=2-s2.0-0036180897&partnerID=40&md5=22cebec3de008eb7de64cbe1d9f9e37f
Date Issue: 2002
Appears in Collections:Unicamp - Artigos e Outros Documentos

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