A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring
Size

J 2013

A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size

KAMMATH, Viju Balachandran; Tomáš ŠOLOMEK; Bokolombe Pitchou NGOY; Dominik HEGER; Petr KLÁN et al.

Základní údaje

Originální název

A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size

Autoři

KAMMATH, Viju Balachandran; Tomáš ŠOLOMEK; Bokolombe Pitchou NGOY; Dominik HEGER; Petr KLÁN; Marina RUBINA a Richard GIVENS

Vydání

Journal of Organic Chemistry, Columbus, OH, USA, the American Chemical Society, 2013, 0022-3263

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10401 Organic chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.638

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/13:00066104

Organizační jednotka

Přírodovědecká fakulta

DOI

https://doi.org/10.1021/jo300850a

UT WoS

000315707500003

Klíčová slova anglicky

Photochemistry; hydroxyphenacyl; ring contraction

Štítky

AKR, rivok

Změněno: 1. 4. 2015 22:12, prof. RNDr. Petr Klán, Ph.D.

Anotace

V originále

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.

Návaznosti

ED0001/01/01, projekt VaV

Název: CETOCOEN

GA203/09/0748, projekt VaV

Název: Nové fotoaktivovatelné sloučeniny pro organickou chemii a biologii

Investor: Grantová agentura ČR, Nové fotoaktivovatelné sloučeniny pro organickou chemii a biologii

ME09021, projekt VaV

Název: Vývoj nových fotoaktivovatelných systémů pro biologické studie

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Vývoj nových fotoaktivovatelných systémů pro biologické studie, Program výzkumu a vývoje KONTAKT (ME)

Citovat

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. 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://doi.org/10.1021/jo300850a.

@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 = {https://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://doi.org/10.1021/jo300850a.

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