About: Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group

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About: Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
rdfs:seeAlso	http://dx.doi.org/10.1021/jo400460x
Description	A detailed experimental and DFT study of the S to N alkyl migration of substituted S-(1(3H)-isobenzofuranon-3-yl)isothiuronium bromide to N,N'-dimethyl-N-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)thiourea provided evidence for the existence of an unusual double displacement mechanism involving two consecutive back-side S(N)2 reactions where a carboxylate anion has a crucial role both as a leaving group as well as an internal nucleophile. The thiazetidine zwitterionic species that is involved in this mechanism as an intermediate was characterized by infrared multiphoton dissociation spectroscopy and was trapped with methyl iodide. It was found that the intermediate has a structure of a free ion pair. The double-displacement mechanism can be considered as a new type of inverse lactone neighboring group participation. A detailed experimental and DFT study of the S to N alkyl migration of substituted S-(1(3H)-isobenzofuranon-3-yl)isothiuronium bromide to N,N'-dimethyl-N-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)thiourea provided evidence for the existence of an unusual double displacement mechanism involving two consecutive back-side S(N)2 reactions where a carboxylate anion has a crucial role both as a leaving group as well as an internal nucleophile. The thiazetidine zwitterionic species that is involved in this mechanism as an intermediate was characterized by infrared multiphoton dissociation spectroscopy and was trapped with methyl iodide. It was found that the intermediate has a structure of a free ion pair. The double-displacement mechanism can be considered as a new type of inverse lactone neighboring group participation. (en)
Title	Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group (en)
skos:prefLabel	Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group Inverse Neighboring Group Participation: Explanation of an Unusual S -> N Alkyl Migration of lsothiuronium Salts Containing a Lactone Group (en)
skos:notation	RIV/00216208:11310/13:10159277!RIV14-GA0-11310___
http://linked.open...avai/riv/aktivita	P S
http://linked.open...avai/riv/aktivity	P(EE2.3.30.0021), P(GAP207/11/0338), S
http://linked.open...iv/cisloPeriodika	9
http://linked.open...vai/riv/dodaniDat	2014
http://linked.open...aciTvurceVysledku	Roithová, Jana Škríba, Anton Jašík, Juraj
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	Univerzita Karlova v Praze / Přírodovědecká fakulta
http://linked.open...dnocenehoVysledku	81052
http://linked.open...ai/riv/idVysledku	RIV/00216208:11310/13:10159277
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	s(N)2 reactions; mass-spectrometry; transition-states; s-acylisothioureas; enzymatic-reactions; nucleophilic-substitution; gas-phase; n acyl migration; degenerate ring transformations; identity substitution-reactions (en)
http://linked.open.../riv/klicoveSlovo	degenerate ring transformations identity substitution-reactions n acyl migration s(N)2 reactions s-acylisothioureas transition-states gas-phase enzymatic-reactions mass-spectrometry nucleophilic-substitution
http://linked.open...odStatuVydavatele	CH - Švýcarská konfederace
http://linked.open...ontrolniKodProRIV	[84286C736010]
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	7 (xsd:int)
http://linked.open...vavai/riv/projekt	Strenthening of Research and Development Teams at the University of Pardubice Reaction mechanisms in organometallic chemistry
http://linked.open...UplatneniVysledku	2013
http://linked.open...v/svazekPeriodika	78
http://linked.open...iv/tvurceVysledku	Váňa, Jiří Sedlák, Miloš Hanusek, Jiří Roithová, Jana Jašík, Juraj Škríba, Anton Kammel, Richard
http://linked.open...ain/vavai/riv/wos	000318588800027
issn	0022-3263
number of pages	7 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/jo400460x
http://localhost/t...ganizacniJednotka	11310

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