Detailed Information on Publication Record
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:
Impact factor
Impact factor: 4.785
RIV identification code
RIV/00216224:14310/15:00081137
Organization unit
Faculty of Science
UT WoS
000362386400034
Keywords in English
photochemistry; ammonium salts; photoremovable protecting group
Změněno: 11/2/2016 14:08, prof. RNDr. Petr Klán, Ph.D.
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 |
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LM2011028, research and development project |
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LO1214, research and development project |
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