Discovery and Comparison of Homogeneous Catalysts in a Standardized HOT‐CAT Screen with Microwave‐Heating and qNMR Analysis: Exploring Catalytic Hydration of Alkynes,ChemCatChem

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Discovery and Comparison of Homogeneous Catalysts in a Standardized HOT‐CAT Screen with Microwave‐Heating and qNMR Analysis: Exploring Catalytic Hydration of Alkynes
ChemCatChem ( IF 3.8 ) Pub Date : 2019-11-27 , DOI: 10.1002/cctc.201900456
Matthias Schreyer _{1,

2} , Tobias M. Milzarek ₁ , Marcus Wegmann _{1,

2} , Andreas Brunner ₁ , Lukas Hintermann _{1,

2}

Affiliation

A HOT‐CAT (homogeneous thermal catalysis) screen using microwave‐heating and quantitative NMR (qNMR) analysis has been developed for identification and comparison of catalyst activity in homogeneous metal‐based catalysis. The hydration of terminal alkynes to ketones or aldehydes served as a model reaction in this proof‐of‐concept study. Key aspects of the screen are the use of a high‐temperature setting (e. g., 160 °C) at a fixed, short reaction time (e. g., 15 min) for all samples. Analysis of crude reaction mixtures by a standardized, quantitative ¹H NMR protocol gives a comprehensive picture of catalyst chemo‐ and regioselectivity, which permits broad comparisons and the discovery of non‐target reactivity. For catalytic alkyne hydration, data for 105 runs involving 81 catalyst systems with 15 different metals is presented. The activity of all established catalyst systems was reproduced, and new catalyst systems with Markovnikov hydration selectivity were discovered and applied to preparative runs, namely Cu₂O−CSA (CSA=camphorsulfonic acid), Co(OAc)₂−tetraphenylporphyrin−CSA and [IrCl(COD)]−CSA.

中文翻译：

在采用微波加热和qNMR分析的标准化HOT-CAT屏幕中发现和比较均相催化剂：探索炔烃的催化水合反应

已开发出一种利用微波加热和定量NMR（qNMR）分析的HOT-CAT（均相热催化）屏幕，用于鉴定和比较均相金属催化中的催化剂活性。在此概念验证研究中，末端炔烃水合为酮或醛可作为模型反应。屏幕的关键方面是在所有样品的固定，短反应时间（例如15分钟）内使用高温设置（例如160°C）。通过标准化的定量分析¹对粗反应混合物进行分析1 H NMR方案提供了催化剂化学和区域选择性的全面描述，可进行广泛的比较和发现非目标反应性。对于炔烃催化水合，给出了涉及81种含15种不同金属的催化剂体系的105次运行数据。复制了所有已建立的催化剂体系的活性，发现了具有马尔可夫尼科夫水合选择性的新型催化剂体系，并将其应用于制备性实验，即Cu ₂ O-CSA（CSA =樟脑磺酸），Co（OAc）_2-四苯基卟啉-CSA和[ IrCl（COD）]-CSA。

更新日期：2019-11-28

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