Discovery and Preclinical Sciences, Process & Analytical Chemistry - Structure Elucidation Group, Merck Research Laboratories, Summit, NJ 07901, USA.
Magn Reson Chem. 2012 Nov;50(11):722-8. doi: 10.1002/mrc.3870. Epub 2012 Sep 19.
Establishing the carbon skeleton of a molecule greatly facilitates the process of structure elucidation, leaving only heteroatoms to be inserted, heterocyclic rings to be closed, and stereochemical features to be defined. INADEQUATE, and more recently PANACEA, have been the only means of coming close to the goal of totally defining the carbon skeleton of a molecule. Unfortunately, the extremely low sensitivity and prodigious sample requirements of these experiments and the multiple receiver requirement for the latter experiment have severely restricted the usage of these experiments. Proton-detected ADEQUATE experiments, in contrast, have considerably higher sensitivity and more modest sample requirements. By combining experiments such as 1,1-ADEQUATE and 1,n-ADEQUATE with higher sensitivity experiments such as GHSQC through covariance processing, sample requirements can be further reduced with a commensurate improvement in the s/n ratio and F(1) resolution of the covariance processed spectrum. We now wish to report the covariance processing of an inverted (1)J(CC) 1,n-ADEQUATE experiment with a non-edited GHSQC spectrum to afford a spectrum that can trace the carbon skeleton of a molecule with the exception of correlations between quaternary carbons.
建立分子的碳骨架极大地促进了结构解析的过程,只剩下杂原子需要插入,杂环需要封闭,以及立体化学特征需要定义。INEQUATE 和最近的 PANACEA 一直是接近完全定义分子碳骨架目标的唯一手段。不幸的是,这些实验的极低灵敏度和巨大的样品需求以及后一个实验的多个接收器要求严重限制了这些实验的使用。相比之下,质子检测的 ADEQUATE 实验具有更高的灵敏度和更适中的样品需求。通过将 1,1-ADEQUATE 和 1,n-ADEQUATE 等实验与更高灵敏度的实验(如 GHSQC)结合使用,并通过协方差处理进行组合,可以进一步减少样品需求,同时提高协方差处理谱的 s/n 比和 F(1)分辨率。我们现在希望报告使用未编辑的 GHSQC 谱对倒置(1)J(CC) 1,n-ADEQUATE 实验进行协方差处理,以提供一个可以追踪分子碳骨架的谱,除了四元碳之间的相关性。