Wu Danni, Carillo Kathleen Joyce, Shie Jiun-Jie, Yu Steve S-F, Tzou Der-Lii M
Institute of Chemistry, Academia Sinica, Nankang, Taipei 11529, Taiwan.
International Graduate Program, SCST, Academia Sinica, Nankang, Taipei 11529, Taiwan.
Molecules. 2021 Apr 30;26(9):2643. doi: 10.3390/molecules26092643.
For decades, high-resolution H NMR spectroscopy has been routinely utilized to analyze both naturally occurring steroid hormones and synthetic steroids, which play important roles in regulating physiological functions in humans. Because the H signals are inevitably superimposed and entangled with various splitting patterns, such that the individual H chemical shift and associated coupling identities are hardly resolved. Given this, applications of thess information for elucidating steroidal molecular structures and steroid/ligand interactions at the atomic level were largely restricted. To overcome, we devoted to unraveling the entangled splitting patterns of two similar steroidal compounds having fully unsaturated protons, i.e., androstanolone and epiandrosterone (denoted as and , respectively), in which only hydroxyl and ketone substituents attached to C3 and C17 were interchanged. Here we demonstrated that the values deduced from and are universal and applicable to other steroids, such as testosterone, 3β, 21-dihydroxygregna-5-en-20-one, prednisolone, and estradiol. On the other hand, the H chemical shifts may deviate substantially from sample to sample. In this communication, we propose a simple but novel scheme for resolving the complicate splitting patterns and H chemical shifts, aiming for steroidal structure determinations.
几十年来，高分辨率氢核磁共振光谱法一直被常规用于分析天然存在的甾体激素和合成甾体，这些甾体在调节人体生理功能中发挥着重要作用。由于氢信号不可避免地与各种分裂模式叠加和纠缠在一起，以至于单个氢化学位移和相关的耦合特性几乎无法分辨。鉴于此，这些信息在原子水平上用于阐明甾体分子结构和甾体/配体相互作用的应用在很大程度上受到限制。为了克服这一问题，我们致力于解开两种具有完全不饱和质子的相似甾体化合物（即雄甾烷醇和表雄甾酮，分别表示为 和 ）的纠缠分裂模式，其中仅连接在C3和C17上的羟基和酮取代基相互交换。在这里我们证明，从 和 推导出的值是通用的，适用于其他甾体，如睾酮、3β,21 - 二羟基孕甾 - 5 - 烯 - 20 - 酮、泼尼松龙和雌二醇。另一方面，氢化学位移可能因样品而异。在本通讯中，我们提出了一种简单但新颖的方案来解析复杂的分裂模式和氢化学位移，旨在进行甾体结构测定。
