4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting
Group for Amines in Aqueous Solutions

J 2015

4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions

BOWNIK, Iwona Božena; Peter ŠEBEJ; Jaromír LITERÁK; Dominik HEGER; Zdeněk ŠIMEK et. al.

Základní údaje

Originální název

4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions

Autoři

BOWNIK, Iwona Božena; Peter ŠEBEJ; Jaromír LITERÁK; Dominik HEGER; Zdeněk ŠIMEK; Richard S. GIVENS a Petr KLÁN

Vydání

The Journal of Organic Chemistry, ACS Publications, 2015, 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: 4.785

Kód RIV

RIV/00216224:14310/15:00081137

Organizační jednotka

Přírodovědecká fakulta

DOI

https://doi.org/10.1021/acs.joc.5b01770

UT WoS

000362386400034

EID Scopus

2-s2.0-84942906332

Klíčová slova anglicky

photochemistry; ammonium salts; photoremovable protecting group

Štítky

AKR, rivok

Změněno: 11. 2. 2016 14:08, prof. RNDr. Petr Klán, Ph.D.

Anotace

V originále

Irradiation of N-protected p-hydroxyphenacyl (pHP) ammonium caged derivatives at 313 nm releases primary and secondary amines or ammonia in nearly quantitative yields via the photo-Favorskii reaction when conducted in acidic or neutral aqueous buffered media. The reaction efficiencies are strongly dependent on the pH with the most efficient and highest yields obtained when the pH of the media maintains the ammonium and p-hydroxyl groups as their conjugate acids. For example, the overall quantum yields of simple secondary amines release are 0.5 at acidic pH from 3.9 to 6.6 dropping to 0.1 at neutral pH 7.0 and 0.01 at pH 8.4. Speciation studies provide an acid-base profile that helps define the scope and limitations of the reaction. When the pK(a) of the ammonium group is lower than that of the phenolic hydroxyl group, as is the case for the alpha-amino-protected amino acids, the more acidic ammonium ion deprotonates as the media pH is changed from acidic toward neutral or basic, thus diminishing the leaving group ability of the amino group. This, in turn, lowers the propensity for the photo-Favorskii rearrangement reaction to occur and opens the reaction pathway to alternative competing photoreduction process.

Návaznosti

GA13-25775S, projekt VaV

Název: Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

Investor: Grantová agentura ČR, Vývoj viditelným světlem aktivovatelných skupin a fluorescenčních značek pro chemii a biologii

LM2011028, projekt VaV

Název: RECETOX ? Národní infrastruktura pro výzkum toxických látek v prostředí

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, RECETOX Národní infrastruktura pro výzkum toxických látek v prostředí

LO1214, projekt VaV

Název: Centrum pro výzkum toxických látek v prostředí (Akronym: RECETOX)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Centrum pro výzkum toxických látek v prostředí

Citovat

BOWNIK, Iwona Božena; Peter ŠEBEJ; Jaromír LITERÁK; Dominik HEGER; Zdeněk ŠIMEK; Richard S. GIVENS a Petr KLÁN. 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions. The Journal of Organic Chemistry. ACS Publications, 2015, roč. 80, č. 19, s. 9713-9721. ISSN 0022-3263. Dostupné z: https://doi.org/10.1021/acs.joc.5b01770.

@article{1314432,
   author = {Bownik, Iwona Božena and Šebej, Peter and Literák, Jaromír and Heger, Dominik and Šimek, Zdeněk and Givens, Richard S. and Klán, Petr},
   article_number = {19},
   doi = {https://doi.org/10.1021/acs.joc.5b01770},
   keywords = {photochemistry; ammonium salts; photoremovable protecting group},
   language = {eng},
   issn = {0022-3263},
   journal = {The Journal of Organic Chemistry},
   title = {4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions},
   url = {http://pubs.acs.org/doi/10.1021/acs.joc.5b01770},
   volume = {80},
   year = {2015}
}

TY  - JOUR
ID  - 1314432
AU  - Bownik, Iwona Božena - Šebej, Peter - Literák, Jaromír - Heger, Dominik - Šimek, Zdeněk - Givens, Richard S. - Klán, Petr
PY  - 2015
TI  - 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions
JF  - The Journal of Organic Chemistry
VL  - 80
IS  - 19
SP  - 9713-9721
EP  - 9713-9721
PB  - ACS Publications
SN  - 00223263
KW  - photochemistry
KW  - ammonium salts
KW  - photoremovable protecting group
UR  - http://pubs.acs.org/doi/10.1021/acs.joc.5b01770
L2  - http://pubs.acs.org/doi/10.1021/acs.joc.5b01770
N2  - Irradiation of N-protected p-hydroxyphenacyl (pHP) ammonium caged derivatives at 313 nm releases primary and secondary amines or ammonia in nearly quantitative yields via the photo-Favorskii reaction when conducted in acidic or neutral aqueous buffered media. The reaction efficiencies are strongly dependent on the pH with the most efficient and highest yields obtained when the pH of the media maintains the ammonium and p-hydroxyl groups as their conjugate acids. For example, the overall quantum yields of simple secondary amines release are 0.5 at acidic pH from 3.9 to 6.6 dropping to 0.1 at neutral pH 7.0 and 0.01 at pH 8.4. Speciation studies provide an acid-base profile that helps define the scope and limitations of the reaction. When the pK(a) of the ammonium group is lower than that of the phenolic hydroxyl group, as is the case for the alpha-amino-protected amino acids, the more acidic ammonium ion deprotonates as the media pH is changed from acidic toward neutral or basic, thus diminishing the leaving group ability of the amino group. This, in turn, lowers the propensity for the photo-Favorskii rearrangement reaction to occur and opens the reaction pathway to alternative competing photoreduction process.
ER  -

BOWNIK, Iwona Božena; Peter ŠEBEJ; Jaromír LITERÁK; Dominik HEGER; Zdeněk ŠIMEK; Richard S. GIVENS a Petr KLÁN. 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions. \textit{The Journal of Organic Chemistry}. ACS Publications, 2015, roč.~80, č.~19, s.~9713-9721. ISSN~0022-3263. Dostupné z: https://doi.org/10.1021/acs.joc.5b01770.

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