通过优化密度泛函理论（DFT）分析提高J耦合常数在结构研究中的效用。
Enhancing the utility of J coupling constants in structural studies through optimized DFT analysis.
作者信息
Buevich Alexei V, Saurí Josep, Parella Teodor, De Tommasi Nunziatina, Bifulco Giuseppe, Williamson R Thomas, Martin Gary E
机构信息
Structure Elucidation Group, Analytical Research & Development, Merck & Co., Inc., 2015 Galloping Hill Road, Kenilworth, NJ 07033, USA.
出版信息
Chem Commun (Camb). 2019 May 16;55(41):5781-5784. doi: 10.1039/c9cc02469g.
Commonly used DFT methods for the calculation of 1JCH coupling constants have typically required the application of ad hoc correction factors, modification of functionals, or empirical scaling to improve the fit between predicted and experimental values. Here we demonstrate that highly accurate 1JCH coupling predictions can be obtained without such adjustments by careful selection of DFT methods for geometry optimization and J-coupling calculations (e.g. B3LYP/6-31G(d,p)(mixed)//mPW1PW/cc-pVTZ). The proposed method was cross-validated against a diverse set of 122 1JCH couplings and was successfully applied to the conformational and stereochemical analysis of strychnine and a previously unreported trachylobane diterpene natural product.
常用于计算¹JCH耦合常数的密度泛函理论（DFT）方法通常需要应用特殊校正因子、修改泛函或进行经验标度，以提高预测值与实验值之间的拟合度。在此，我们证明，通过仔细选择用于几何优化和J耦合计算的DFT方法（例如B3LYP/6-31G(d,p)(混合)//mPW1PW/cc-pVTZ），无需进行此类调整即可获得高度准确的¹JCH耦合预测。所提出的方法针对122个不同的¹JCH耦合进行了交叉验证，并成功应用于士的宁和一种先前未报道的trachylobane二萜天然产物的构象和立体化学分析。
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