Stereocartography: a computational mapping technique that can locate regions of maximum stereoinduction around chiral catalysts.
Stereocartography: a computational mapping technique that can locate regions of maximum stereoinduction around chiral catalysts.
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立体制图术：一种计算绘图技术，可以定位手性催化剂周围最大立体感应区域。
DOI：
10.1021/ja0207192
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发表时间：
2002
影响因子：
15
通讯作者：
Jonathan Stack
中科院分区：
文献类型：
--
作者：
K. Lipkowitz;Cedric D'Hue;T. Sakamoto;Jonathan Stack
提出了一个关于手性催化剂不对称诱导的假设，并对其进行了验证。该假设认为，在诱导不对称方面效率高的手性催化剂，其最大立体感应区在空间上与化学位置一致，而效率低的催化剂则不然。使用一种简单的映射策略（立体图）来评估最大立体感应区域位于给定催化剂周围的位置。该方案比较了被考虑的催化剂周围空间中每个点的镜像探针之间的相互作用能。探针是由特定催化剂催化的反应的实际过渡态的模型。该假设在三个Diels-Alder反应中得到了验证。18种催化剂中有17种符合这一假设。提出了将其作为催化剂设计工具的想法。
A hypothesis concerning asymmetric induction by chiral catalysts is posited, tested, and found to be valid. The hypothesis states that chiral catalysts that are efficient at inducing asymmetry will have their region of maximum stereoinduction spatially congruent with the site of chemistry but inefficient catalysts will not. A simple mapping strategy (stereocartography) is used to assess where the region of maximum stereoinduction is located around a given catalyst. The protocol compares interaction energies between mirror image probes at each point in space around the catalyst being considered. The probes are models of the actual transition states of the reaction being catalyzed by a particular catalyst. The hypothesis was tested on three Diels-Alder reactions. Seventeen of the eighteen catalysts conform to the hypothesis. The idea of using this as a catalyst design tool is presented.