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Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
多个立体中心的完整相对立体化学,仅使用剩余的二极合
Jiangli Yan1, Frank Delaglio, Andreas Kaerner
1Discovery Chemistry Research and Technologies, Lilly Research Labs, Lilly Corporate Center, Eli Lilly & Company, Indianapolis, Indiana 46285, USA.
Journal of the American Chemical Society
|April 15, 2004
概括
剩余二极合 (RDC) 和顺序矩阵计算精确地确定了有机化合物的立体化学. 这种方法,使用简单的实验,为复杂分子的X射线晶体学提供了可靠的替代方案.
科学领域:
- 有机化学 有机化学
- 结构生物学 结构生物学
- 生物物理化学 生物物理化学
背景情况:
- 确定具有多个立体中心的复杂有机分子的完整相对立体化学是具有挑战性的.
- 剩余二极合器 (RDC) 提供了有价值的长距离结构信息.
- 分子顺序矩阵计算对于解释RDC数据至关重要.
研究的目的:
- 为了明确确定五个立体中心的有机化合物的完整相对立体化学.
- 为了评估RDCs的实用性,与立体化学赋值的顺序矩阵计算相结合.
- 将基于RDC的分配与单晶X射线衍射结果进行比较.
主要方法:
- 测量各种残余二极合 (RDCs),包括 (13) C-(1) H, (13) C-(19) F, (19) F-(1) H和 (1) H-(1) H,使用简单的单维实验.
- 独立的顺序矩阵计算每个性同位素.
- 通过比较计算和测量RDC之间的平方根平均偏差 (rmsd) 来评估匹配.
- 使用来自不同对齐介质 (和双) 的RDC数据进行订单张量模拟.
主要成果:
- 对于五个立体中心的化合物,完全的相对立体化学被明确地确定.
- 来自RDC的立体化学赋值与单晶X射线结构结果完全一致.
- 模拟需要六个RDC;七个提供了可接受的结果.
- (13) C-(1) H 和 (1) H-(1) H RDC 被确定为订单矩阵计算中最有信息的.
- 没有质子的立体中心可以使用附近的RDC数据来分配.
结论:
- 剩余双极合,加上分子顺序矩阵计算,提供了一个完整的立体化学确定强大的方法.
- 这种基于RDC的方法为X射线晶体学提供了一个可行的和准确的替代方案,特别是对于具有挑战性的分子.
- RDCs的选择和位置对立体化学赋值的准确性和效率产生重大影响.
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