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@article{1104117,
author = {Kammath, Viju Balachandran and Šolomek, Tomáš and Ngoy, Bokolombe Pitchou and Heger, Dominik and Klán, Petr and Rubina, Marina and Givens, Richard},
article_location = {Columbus, OH, USA},
article_number = {5},
doi = {http://dx.doi.org/10.1021/jo300850a},
keywords = {Photochemistry; hydroxyphenacyl; ring contraction},
language = {eng},
issn = {0022-3263},
journal = {Journal of Organic Chemistry},
title = {A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size},
url = {http://pubs.acs.org/doi/abs/10.1021/jo300850a},
volume = {78},
year = {2013}
}
TY - JOUR
ID - 1104117
AU - Kammath, Viju Balachandran - Šolomek, Tomáš - Ngoy, Bokolombe Pitchou - Heger, Dominik - Klán, Petr - Rubina, Marina - Givens, Richard
PY - 2013
TI - A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size
JF - Journal of Organic Chemistry
VL - 78
IS - 5
SP - 1718-1729
EP - 1718-1729
PB - the American Chemical Society
SN - 00223263
KW - Photochemistry
KW - hydroxyphenacyl
KW - ring contraction
UR - http://pubs.acs.org/doi/abs/10.1021/jo300850a
N2 - 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. Employing a combination of time-resolved absorption measurements, quantum yield determinations, isotopic labeling, and solvent variation studies coupled with theoretical treatment, a more comprehensive mechanistic description of the rearrangement has emerged.
ER -
KAMMATH, Viju Balachandran, Tomáš ŠOLOMEK, Bokolombe Pitchou NGOY, Dominik HEGER, Petr KLÁN, Marina RUBINA a Richard GIVENS. A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size. \textit{Journal of Organic Chemistry}. Columbus, OH, USA: the American Chemical Society, 2013, roč.~78, č.~5, s.~1718-1729. ISSN~0022-3263. Dostupné z: https://dx.doi.org/10.1021/jo300850a.
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