Investigations via Kinetics and Multivariate Linear Regression Models of the Mechanism and Origins of Regioselectivity in a Palladium-Catalyzed Aryne Annulation

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-10-17 DOI:10.1021/acscatal.4c0487310.1021/acscatal.4c04873

Erin E. Plasek, Brylon N. Denman and Courtney C. Roberts*,

引用次数: 0

Abstract

The synthetic potential of unsymmetrically substituted arynes is not yet fully realized due to regioselectivity issues. Although many models exist to predict the regioselectivity of arynes, these models do not hold for metal-mediated reactions. Previously, we reported a way to induce regioselectivity in a metal-catalyzed aryne annulation reaction by using bulky monodentate phosphine ligands. Reported herein is a mechanistic investigation into the operative catalytic cycle within this transformation. Additionally, the molecular parameters responsible for regioselectivity have been examined via linear free energy relationships and multivariate linear regression. This model shows the interdependence on both the steric and electronic properties of the aryne and the size of the phosphine ligand for regioselectivity.

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通过动力学和多元线性回归模型研究钯催化芳炔嵌合反应的机理和区域选择性的起源

由于存在区域选择性问题，非对称取代芳烃的合成潜力尚未得到充分发挥。虽然有很多模型可以预测芳香烃的区域选择性，但这些模型并不适用于金属介导的反应。以前，我们曾报道过一种通过使用笨重的单齿膦配体在金属催化的芳炔环化反应中诱导区域选择性的方法。本文报告了对这一转化过程中催化循环的机理研究。此外，还通过线性自由能关系和多元线性回归研究了导致区域选择性的分子参数。该模型表明，芳炔的立体和电子特性与膦配体的大小对区域选择性的影响是相互依存的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.