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Statements

Subject Item
n2:RIV%2F00216224%3A14310%2F13%3A00066104%21RIV14-MSM-14310___
rdf:type
n11:Vysledek skos:Concept
dcterms:description
The effect of ring size on the photo-Favorskii induced ring-contraction reaction of the hydroxybenzocycloalkanonyl acetate and mesylate esters (7a–d, 8a–c) has provided new insight into the mechanism of the rearrangement. By monotonically decreasing the ring size in these cyclic derivatives, the increasing ring strain imposed on the formation of the elusive bicyclic spirocyclopropanone 20 results in a divergence away from rearrangement and toward solvolysis. Cycloalkanones of seven or eight carbons undergo a highly efficient photo-Favorskii rearrangement with ring contraction paralleling the photochemistry of p-hydroxyphenacyl esters. In contrast, the five-carbon ring does not rearrange but is diverted to the photosolvolysis channel avoiding the increased strain energy that would accompany the formation of the spirobicyclic ketone, the “Favorskii intermediate 20”. The six-carbon analogue demonstrates the bifurcation in reaction channels, yielding a solvent-sensitive mixture of both. The effect of ring size on the photo-Favorskii induced ring-contraction reaction of the hydroxybenzocycloalkanonyl acetate and mesylate esters (7a–d, 8a–c) has provided new insight into the mechanism of the rearrangement. By monotonically decreasing the ring size in these cyclic derivatives, the increasing ring strain imposed on the formation of the elusive bicyclic spirocyclopropanone 20 results in a divergence away from rearrangement and toward solvolysis. Cycloalkanones of seven or eight carbons undergo a highly efficient photo-Favorskii rearrangement with ring contraction paralleling the photochemistry of p-hydroxyphenacyl esters. In contrast, the five-carbon ring does not rearrange but is diverted to the photosolvolysis channel avoiding the increased strain energy that would accompany the formation of the spirobicyclic ketone, the “Favorskii intermediate 20”. The six-carbon analogue demonstrates the bifurcation in reaction channels, yielding a solvent-sensitive mixture of both.
dcterms:title
A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size
skos:prefLabel
A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size
skos:notation
RIV/00216224:14310/13:00066104!RIV14-MSM-14310___
n11:predkladatel
n13:orjk%3A14310
n3:aktivita
n16:S n16:P
n3:aktivity
P(ED0001/01/01), P(GA203/09/0748), P(ME09021), S
n3:cisloPeriodika
5
n3:dodaniDat
n10:2014
n3:domaciTvurceVysledku
n6:2247542 n6:1626418 n6:8962855 n6:1594974 Kammath, Viju Balachandran
n3:druhVysledku
n17:J
n3:duvernostUdaju
n9:S
n3:entitaPredkladatele
n14:predkladatel
n3:idSjednocenehoVysledku
58935
n3:idVysledku
RIV/00216224:14310/13:00066104
n3:jazykVysledku
n19:eng
n3:klicovaSlova
Photochemistry; hydroxyphenacyl; ring contraction
n3:klicoveSlovo
n15:hydroxyphenacyl n15:Photochemistry n15:ring%20contraction
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[E65BE7EC04F8]
n3:nazevZdroje
Journal of Organic Chemistry
n3:obor
n12:CC
n3:pocetDomacichTvurcuVysledku
5
n3:pocetTvurcuVysledku
7
n3:projekt
n8:ME09021 n8:ED0001%2F01%2F01 n8:GA203%2F09%2F0748
n3:rokUplatneniVysledku
n10:2013
n3:svazekPeriodika
78
n3:tvurceVysledku
Šolomek, Tomáš Klán, Petr Ngoy, Bokolombe Pitchou Givens, Richard Rubina, Marina Kammath, Viju Balachandran Heger, Dominik
n3:wos
000315707500003
s:issn
0022-3263
s:numberOfPages
12
n20:doi
10.1021/jo300850a
n18:organizacniJednotka
14310