Detailed Information on Publication Record
2009
Photochemistry of 2-Nitrobenzylidene Acetals
ŠEBEJ, Peter, Tomáš ŠOLOMEK, Ľubica HROUDNÁ, Pavla BRANCOVÁ, Petr KLÁN et. al.Basic information
Original name
Photochemistry of 2-Nitrobenzylidene Acetals
Name in Czech
Fotochemie 2-nitrobenzyliden acetalů
Authors
ŠEBEJ, Peter (703 Slovakia), Tomáš ŠOLOMEK (703 Slovakia), Ľubica HROUDNÁ (703 Slovakia), Pavla BRANCOVÁ (203 Czech Republic) and Petr KLÁN (203 Czech Republic, guarantor)
Edition
Journal of Organic Chemistry, Columbus, OH, USA, the American Chemical Society, 2009, 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
Impact factor
Impact factor: 4.219
RIV identification code
RIV/00216224:14310/09:00029556
Organization unit
Faculty of Science
UT WoS
000271662500018
Keywords in English
Photochemistry; Photoremovable protecting groups
Tags
International impact, Reviewed
Změněno: 13/11/2009 14:41, prof. RNDr. Petr Klán, Ph.D.
V originále
Photolysis of dihydroxy compounds (diols) protected as 2-nitrobenzylidene acetals (ONBA) and subsequent acid- or base-catalyzed hydrolysis of the 2-nitrosobenzoic acid ester intermediates result in an efficient and high-yielding release of the substrates. We investigated the scope and limitations of ONBA photochemistry and expanded upon earlier described two-step procedures to show that the protected diols of many structural varieties can also be liberated in a one-pot procedure. In view of the fact that the acetals of nonsymmetrically substituted diols are converted into one of the corresponding 2-nitrosobenzoic acid ester isomers with moderate to high regioselectivity, the mechanism of their formation was studied using various experimental techniques. The experimental data were found to be in agreement with DFT-based quantum chemical calculations that showed the preferential cleavage occurs on the acetal C-O bond in the vicinity of more electron-withdrawing (or less electron-donating) groups. The study also revealed considerable complexity in the cleavage mechanism and that the structural variations in the substrate can significantly alter the reaction pathway. This deprotection strategy was found to be also applicable for 2-thioethanol when released from the corresponding monothioacetal in the presence of a reducing agent, such as ascorbic acid.
In Czech
Článek popisuje fotolýzu dihydroxy sloučenin (diolů), které jsou chráněny jako 2-benzylidinacetaly a následnou kyselou nebo bazickou hydrolýzu za uvolnění chráněného substrátu.
Links
| GA203/09/0748, research and development project |
| ||
| MSM0021622413, plan (intention) |
|