利用金（I）催化揭示膦配体的细微效应
Uncovering Subtle Ligand Effects of Phosphines Using Gold(I) Catalysis.
作者信息
Christian Alec H, Niemeyer Zachary L, Sigman Matthew S, Toste F Dean
机构信息
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States.
出版信息
ACS Catal. 2017 Jun 2;7(6):3973-3978. doi: 10.1021/acscatal.7b00757. Epub 2017 May 10.
Abstract
Herein, we report the integration of simple linear regressions with gold(I) catalysis to interrogate the influence of phosphine structure on metal-catalyzed organic transformations. We demonstrate that observed product ratios in [4 + 3]/[4 + 2] cycloisomerization processes are influenced by both steric and electronic properties of the phosphine, which can be represented by the Au-Cl distance. In contrast, the observed selectivity of a similar [2 + 3]/[2 + 2] cycloisomerization is governed by L/B1, a steric parameter. Using this correlation, we were able to accurately predict the selectivity of a previously untested, Buchwald-type ligand to enhance selectivity for the same transformation. This ligand found further utility in increasing the selectivity of a previously reported gold-catalyzed cycloisomerization/arylation of 1,6-enynes by ~1 kcal/mol.
摘要
在此，我们报告了简单线性回归与金（I）催化的整合，以研究膦结构对金属催化有机转化的影响。我们证明，在[4 + 3]/[4 + 2]环异构化过程中观察到的产物比例受膦的空间和电子性质影响，这可以用金 - 氯距离来表示。相比之下，类似的[2 + 3]/[2 + 2]环异构化观察到的选择性由空间参数L/B1决定。利用这种相关性，我们能够准确预测一种先前未经测试的布赫瓦尔德型配体的选择性，以提高同一转化反应的选择性。该配体在将先前报道的1,6 - 烯炔的金催化环异构化/芳基化选择性提高约1千卡/摩尔方面进一步发挥了作用。
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