Detailed Information on Publication Record
2007
2,5-Dimethylphenacyl carbamate: A photoremovable protecting group for amines and amino acids
KAMMARI, Laxminarayana, Lukáš PLÍŠTIL, Jakob WIRZ and Petr KLÁNBasic information
Original name
2,5-Dimethylphenacyl carbamate: A photoremovable protecting group for amines and amino acids
Name in Czech
2,5-Dimethylfenacylkarbamát jako fotoodštěpitelná chránicí skupina pro aminy a aminokyseliny
Authors
KAMMARI, Laxminarayana (356 India), Lukáš PLÍŠTIL (203 Czech Republic), Jakob WIRZ (756 Switzerland) and Petr KLÁN (203 Czech Republic, guarantor)
Edition
Photochemical and Photobiological Sciences, Cambridge, United Kingdom, Royal Society of Chemistry, 2007, 1474-905X
Other information
Language
English
Type of outcome
Článek v odborném periodiku
Field of Study
10401 Organic chemistry
Country of publisher
United Kingdom of Great Britain and Northern Ireland
Confidentiality degree
není předmětem státního či obchodního tajemství
Impact factor
Impact factor: 2.208
RIV identification code
RIV/00216224:14310/07:00020037
Organization unit
Faculty of Science
UT WoS
000243204700005
Keywords in English
Photochemistry; photoremovable protecting groups; amines; amino acids
Tags
International impact, Reviewed
Změněno: 23/6/2009 15:13, prof. RNDr. Petr Klán, Ph.D.
V originále
2,5-Dimethylphenacyl (DMP) carbamates (1a-c) released the corresponding free amines or amino acid in high chemical yields, albeit with quantum yields of only 0.04-0.09, upon irradiation in either aprotic or protic solvents. The photoreaction proceeded principally from the triplet excited state via the E-photoenol. The lifetimes of the triplet enol and of the E- and Z-enols in the ground state were determined by laser flash photolysis. The primary photoinitiated transformation liberated a carbamic acid derivative, which subsequently decarboxylated to the amino group containing compound. Exhaustive irradiation of a DMP-protected aniline (1a) in acetonitrile did not provide aniline in quantitative chemical yields, because it was involved in reductive cleavage of the starting material as an electron donor, thereby decreasing the overall deprotection yield (86%). Phenylalanine methyl ester, liberated from 1c, was, however, obtained in excellent chemical yields (97%). It was also found that the carbamates, while thermally stable, released amines with higher quantum yields in acidic methanol solutions. The DMP chromophore is proposed as an excellent photoremovable protecting group for amino acids and, under specific conditions, also for amines in organic synthesis and biochemistry.
In Czech
2,5-Dimethylphenacyl (DMP) carbamates (1a-c) released the corresponding free amines or amino acid in high chemical yields, albeit with quantum yields of only 0.04-0.09, upon irradiation in either aprotic or protic solvents. The photoreaction proceeded principally from the triplet excited state via the E-photoenol. The lifetimes of the triplet enol and of the E- and Z-enols in the ground state were determined by laser flash photolysis. The primary photoinitiated transformation liberated a carbamic acid derivative, which subsequently decarboxylated to the amino group containing compound. Exhaustive irradiation of a DMP-protected aniline (1a) in acetonitrile did not provide aniline in quantitative chemical yields, because it was involved in reductive cleavage of the starting material as an electron donor, thereby decreasing the overall deprotection yield (86%). Phenylalanine methyl ester, liberated from 1c, was, however, obtained in excellent chemical yields (97%). It was also found that the carbamates, while thermally stable, released amines with higher quantum yields in acidic methanol solutions. The DMP chromophore is proposed as an excellent photoremovable protecting group for amino acids and, under specific conditions, also for amines in organic synthesis and biochemistry.
Links
| GA203/05/0641, research and development project |
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| MSM0021622413, plan (intention) |
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