Monitoring mechanistic details in the synthesis of pyrimidines via real-time, ultrafast multidimensional NMR spectroscopy.
Monitoring mechanistic details in the synthesis of pyrimidines via real-time, ultrafast multidimensional NMR spectroscopy.
复制标题
DOI：
10.1021/ja210154g
复制
发表时间：
2012-02-08
影响因子：
15
通讯作者：
Herrera, Antonio
中科院分区：
文献类型：
--
作者：
Pardo, Zulay D.;Olsen, Gregory L.;Encarnacion Fernandez-Valle, Maria;Frydman, Lucio;Martinez-Alvarez, Roberto;Herrera, Antonio
Recent years have witnessed unprecedented advances in the development of fast multidimensional NMR acquisition techniques. This progress could open valuable new opportunities for the elucidation of chemical and biochemical processes. This study demonstrates one such capability, with the first real-time 2D dynamic analysis of a complex organic reaction relying on unlabeled substrates. Implementing such measurements required the development of new ultrafast 2D methods, capable of monitoring multiple spectral regions of interest as the reaction progressed. The alternate application of these acquisitions in an interleaved, excitation-optimized fashion, allowed us to extract new structural and dynamic insight concerning the reaction between aliphatic ketones and triflic anhydride in the presence of nitriles to yield alkylpyrimidines. Up to 2500 2D NMR data sets were thus collected over the course of this nearly 100 min long reaction, in an approach resembling that used in functional magnetic resonance imaging. With the aid of these new frequency-selective low-gradient-strength experiments, supplemented by chemical shift calculations of the spectral coordinates observed in the 2D heteronuclear correlations, previously postulated intermediates involved in the alkylpyrimidine formation process could be confirmed, and hitherto undetected ones were revealed. The potential and limitations of the resulting methods are discussed.
登录
查看更多内容
影响因子：
15
作者：
Gal, M;Mishkovsky, M;Frydman, L
通讯作者：
Frydman, L
DOI：
10.1039/b102014p
发表时间：
2001-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
Darbeau, RW;Gibble, RE;Heurtin, DJ
通讯作者：
Heurtin, DJ
影响因子：
3.6
作者：
Herrera, A;Martínez-Alvarez, R;Torres, R
通讯作者：
Torres, R
影响因子：
2.1
作者：
Herrera, A;Martínez-Alvarez, R;Sánchez, A
通讯作者：
Sánchez, A
影响因子：
2.1
作者：
Herrera, Antonio;Martinez-Alvarez, Roberto;Almy, John
通讯作者：
Almy, John