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.

Basic information

Original name

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

Authors

BOWNIK, Iwona Božena (616 Poland, belonging to the institution), Peter ŠEBEJ (703 Slovakia, belonging to the institution), Jaromír LITERÁK (203 Czech Republic, belonging to the institution), Dominik HEGER (203 Czech Republic, belonging to the institution), Zdeněk ŠIMEK (203 Czech Republic, belonging to the institution), Richard S. GIVENS (840 United States of America) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

The Journal of Organic Chemistry, ACS Publications, 2015, 0022-3263

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.785

RIV identification code

RIV/00216224:14310/15:00081137

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.joc.5b01770

UT WoS

000362386400034

Keywords in English

photochemistry; ammonium salts; photoremovable protecting group

Abstract

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.

Links

GA13-25775S, research and development project

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

Investor: Czech Science Foundation

LM2011028, research and development project

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

Investor: Ministry of Education, Youth and Sports of the CR

LO1214, research and development project

Name: Centrum pro výzkum toxických látek v prostředí (Acronym: RECETOX)

Investor: Ministry of Education, Youth and Sports of the CR

Citovat

BOWNIK, Iwona Božena, Peter ŠEBEJ, Jaromír LITERÁK, Dominik HEGER, Zdeněk ŠIMEK, Richard S. GIVENS and Petr KLÁN. 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions. The Journal of Organic Chemistry. ACS Publications, 2015, vol. 80, No 19, p. 9713-9721. ISSN 0022-3263. Available from: https://dx.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 = {http://dx.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 and Petr KLÁN. 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions. \textit{The Journal of Organic Chemistry}. ACS Publications, 2015, vol.~80, No~19, p.~9713-9721. ISSN~0022-3263. Available from: https://dx.doi.org/10.1021/acs.joc.5b01770.

Detailed Information on Publication Record