金属催化的芳炔反应区域选择性研究
Insights into the Regioselectivity of Metal-Catalyzed Aryne Reactions.
作者信息
Plasek Erin E, Denman Brylon N, Roberts Courtney C
机构信息
University of Minnesota, Department of Chemistry, 225 Pleasant Street SE, Minneapolis, MN 55455, USA.
出版信息
Synlett. 2024 Apr;35(7):747-752. doi: 10.1055/s-0042-1751487. Epub 2023 Sep 18.
Abstract
The synthetic potential of unsymmetrically substituted aryne intermediates is significantly hindered by regioselectivity issues. Current methods for inducing regioselectivity all rely on substrate control and are focused on non-metallated arynes. Before our initial disclosure, there was no systematic study regarding the regioselectivity of metal-catalyzed aryne reactions. By exploiting ligand control, we have induced regioselectivity in a palladium-catalyzed aryne annulation to form phenanthridinones (up to 9:91 r.r.). Through this study we have investigated: ligand effects, influence of steric perturbation, and the impact of the aryne precursor.
摘要
不对称取代的芳炔中间体的合成潜力受到区域选择性问题的显著阻碍。目前诱导区域选择性的方法都依赖于底物控制，并且集中在未金属化的芳炔上。在我们首次披露之前，没有关于金属催化芳炔反应区域选择性的系统研究。通过利用配体控制，我们在钯催化的芳炔环化反应中诱导了区域选择性，以形成菲啶酮（区域选择性最高可达9:91）。通过这项研究，我们研究了：配体效应、空间扰动的影响以及芳炔前体的影响。
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