Flash photolytic release of alcohols from photolabile carbamates or carbonates is rate-limited by decarboxylation of the photoproduct

被引：33

作者：

Papageorgiou, G

Barth, A

Corrie, JET

机构：

[1] Natl Inst Med Res, Ridgeway, London NW7 1AA, England

[2] Stockholm Univ, Arrhenius Labs Nat Sci, Dept Biochem & Biophys, SE-10691 Stockholm, Sweden

来源：

PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES | 2005年 / 4卷 / 02期

基金：

英国医学研究理事会;

关键词：

D O I：

10.1039/b417153e

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Flash photolysis of a 7-nitroindolinyl carbamate derivative in neutral aqueous solution rapidly generated a monoalkyl carbonate salt. The rate constant for subsequent decarboxylation of this salt [mono(2-phosphoryloxyethyl) carbonate], determined by rapid scan IR difference spectroscopy, was 0.4 s(-1) at pH 7.0, 20degreesC. This rate reflects release of the product alcohol upon photolysis of the parent compound. In general, alcohols protected as photolabile carbamate (or carbonate) derivatives will therefore be released too slowly for studies of the kinetics of millisecond time scale biological processes.

引用

收藏

页码：216 / 220

页数：5

相关论文

共 31 条

[1] Photo-removable protecting groups for in situ DNA microarray synthesis [J].

Afroz, F ;

Barone, AD ;

Bury, PA ;

Chen, CA ;

Cuppoletti, A ;

Kuimelis, RG ;

Li, HD ;

McGall, GH .

CLINICAL CHEMISTRY, 2004, 50 (10) :1936-1939

[2] A CONVENIENT METHOD FOR THE CONVERSION OF HALIDES TO ALCOHOLS [J].

ALEXANDER, J ;

RENYER, ML ;

VEERAPANANE, H .

SYNTHETIC COMMUNICATIONS, 1995, 25 (23) :3875-3881

[3] Photoreleasable protecting groups based on electron transfer chemistry. Donor sensitized release of phenacyl groups from alcohols, phosphates and diacids [J].

Banerjee, A ;

Lee, K ;

Falvey, DE .

TETRAHEDRON, 1999, 55 (44) :12699-12710

[4] PHOTOCHEMICAL RELEASE OF ATP FROM CAGED-ATP STUDIED BY TIME-RESOLVED INFRARED-SPECTROSCOPY [J].

BARTH, A ;

HAUSER, K ;

MANTELE, W ;

CORRIE, JET ;

TRENTHAM, DR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (41) :10311-10316

[5]

BARTH A, UNPUB

[6]

BUTLER JN, 1982, CARBON DIOXIDE EQUIL, P21

[7]

COLTHUP NB, 1975, INTRO INFRARED RAMAN, P303

[8] Photolytic cleavage of 1-(2-nitrophenyl)ethyl ethers involves two parallel pathways and product release is rate-limited by decomposition of a common hemiacetal intermediate [J].

Corrie, JET ;

Barth, A ;

Munasinghe, VRN ;

Trentham, DR ;

Hutter, MC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (28) :8546-8554

[9] Anthraquinon-2-ylmethoxycarbonyl (Aqmoc): A new photochemically removable protecting group for alcohols [J].

Furuta, T ;

Hirayama, Y ;

Iwamura, M .

ORGANIC LETTERS, 2001, 3 (12) :1809-1812

[10] New photolabile protecting groups in nucleoside and nucleotide chemistry -: Synthesis, cleavage mechanisms and applications [J].

Giegrich, H ;

Eisele-Bühler, S ;

Hermann, C ;

Kvasyuk, E ;

Charubala, R ;

Pfleiderer, W .

NUCLEOSIDES & NUCLEOTIDES, 1998, 17 (9-11) :1987-1996

← 1 2 3 4 →