About: Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	1,3-Dipolar cycloaddition reactions of dihydro-3-methylene-2(3H)-furanone (Tulipalin A) with various benzonitrile(p-X-benzylide) ylides prefer formation of exo-cycloadducts in the extent of corresponding to an increasing electron donor character of the substituent X in p-position of benzylide phenyl ring of 1,3-dipolar reagent. The substituent effect on diastereoselectivity of the 1,3-DC reaction is rationalized in terms of CH/p interaction between dipole and dipolarophile in an exo-transition state. The interaction is demonstrated by the correlation of the observed diastereoselectivities with substituent Hammett sigma constants, which shows a small negative r value. A certain contribution of CO/p interaction between lactone carbonyl and the substituted phenyl ring to mediation of the substituent effect is also discussed. The energy profiles of both reaction pathways were analyzed using DFT and RI-MP2 theoretical approaches. 1,3-Dipolar cycloaddition reactions of dihydro-3-methylene-2(3H)-furanone (Tulipalin A) with various benzonitrile(p-X-benzylide) ylides prefer formation of exo-cycloadducts in the extent of corresponding to an increasing electron donor character of the substituent X in p-position of benzylide phenyl ring of 1,3-dipolar reagent. The substituent effect on diastereoselectivity of the 1,3-DC reaction is rationalized in terms of CH/p interaction between dipole and dipolarophile in an exo-transition state. The interaction is demonstrated by the correlation of the observed diastereoselectivities with substituent Hammett sigma constants, which shows a small negative r value. A certain contribution of CO/p interaction between lactone carbonyl and the substituted phenyl ring to mediation of the substituent effect is also discussed. The energy profiles of both reaction pathways were analyzed using DFT and RI-MP2 theoretical approaches. (en)
Title	Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides (en)
skos:prefLabel	Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides (en)
skos:notation	RIV/00216224:14310/08:00033644!RIV10-MSM-14310___
http://linked.open...avai/riv/aktivita	S Z
http://linked.open...avai/riv/aktivity	S, Z(MSM6198959218)
http://linked.open...iv/cisloPeriodika	8
http://linked.open...vai/riv/dodaniDat	2010
http://linked.open...aciTvurceVysledku	Melša, Petr Mazal, Ctibor Čajan, Michal
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Masarykova univerzita / Přírodovědecká fakulta
http://linked.open...dnocenehoVysledku	398275
http://linked.open...ai/riv/idVysledku	RIV/00216224:14310/08:00033644
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	CH-pi Interaction; Substituent effect; stereoselectivity; cycloaddition (en)
http://linked.open.../riv/klicoveSlovo	CH-pi Interaction Substituent effect stereoselectivity cycloaddition
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[DDCFA193F625]
http://linked.open...i/riv/nazevZdroje	Journal of Organic Chemistry
http://linked.open...in/vavai/riv/obor	CC
http://linked.open...ichTvurcuVysledku	3 (xsd:int)
http://linked.open...cetTvurcuVysledku	4 (xsd:int)
http://linked.open...UplatneniVysledku	2008
http://linked.open...v/svazekPeriodika	73
http://linked.open...iv/tvurceVysledku	Mazal, Ctibor Čajan, Michal Havlas, Zdeněk Melša, Petr
http://linked.open...ain/vavai/riv/wos	000254883700007
http://linked.open...n/vavai/riv/zamer	Komplexní sloučeniny a oxidy přechodných kovů s využitím v bioaplikacích a nanotechnologiích
issn	0022-3263
number of pages	8 (xsd:int)
http://localhost/t...ganizacniJednotka	14310
is http://linked.open...avai/riv/vysledek of	Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides Substituent Effect on exo Stereoselectivity in the 1,3-Dipolar Cycloaddition Reaction of Tulipalin A with Nitrile Ylides

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