Organic chemistry. A data-intensive approach to mechanistic elucidation applied to chiral anion catalysis.
Organic chemistry. A data-intensive approach to mechanistic elucidation applied to chiral anion catalysis.
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DOI：
10.1126/science.1261043
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发表时间：
2015-02-13
期刊：
影响因子：
--
通讯作者：
Sigman MS
中科院分区：
文献类型：
--
作者：
Milo A;Neel AJ;Toste FD;Sigman MS
化学反应机制的知识可以促进催化剂的优化，但从一个复杂的系统中提取这些知识往往是具有挑战性的。在这里，我们提出了一种数据密集型方法，用于推导和预测应用对映选择性有机反应的机理模型。作为验证案例研究，我们选择了一个分子内脱氢C-N偶联反应，由手性磷酸衍生物催化，其中催化剂-底物结合涉及弱的非共价相互作用。以前对该体系中对映体选择性的结构起源了解甚少。通过系统的物理有机趋势分析，探讨了催化剂和底物取代基的作用。底物和催化剂之间控制对映体选择性的合理相互作用被确定并得到实验支持，表明这种方法可以提供利用机理洞察力优化催化剂设计的有效手段。
Knowledge of chemical reaction mechanisms can facilitate catalyst optimization, but extracting that knowledge from a complex system is often challenging. Here we present a data-intensive method for deriving and then predictively applying a mechanistic model of an enantioselective organic reaction. As a validating case study, we selected an intramolecular dehydrogenative C-N coupling reaction, catalyzed by chiral phosphoric acid derivatives, in which catalyst-substrate association involves weak, non-covalent interactions. Little was previously understood regarding the structural origin of enantioselectivity in this system. Catalyst and substrate substituent effects were probed by systematic physical organic trend analysis. Plausible interactions between the substrate and catalyst that govern enantioselectivity were identified and supported experimentally, indicating that such an approach can afford an efficient means of leveraging mechanistic insight to optimize catalyst design.
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影响因子：
2.9
作者：
Hohenstein, Edward G.;Sherrill, C. David
通讯作者：
Sherrill, C. David
影响因子：
56.9
作者：
Santanilla, Alexander Buitrago;Regalado, Erik L.;Dreher, Spencer D.
通讯作者：
Dreher, Spencer D.
影响因子：
64.8
作者：
Milo, Anat;Bess, Elizabeth N.;Sigman, Matthew S.
通讯作者：
Sigman, Matthew S.
DOI：
10.1126/science.1207922
发表时间：
2011-09-09
期刊：
Science (New York, N.Y.)
影响因子：
--
作者：
Robbins DW;Hartwig JF
通讯作者：
Hartwig JF
影响因子：
56.9
作者：
Friedfeld, Max R.;Shevlin, Michael;Chirik, Paul J.
通讯作者：
Chirik, Paul J.