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钯(II)-NHC 配合物催化仲苄醇的无受体脱氢反应生成高附加值酮。

Catalytic Acceptorless Dehydrogenation (CAD) of Secondary Benzylic Alcohols into Value-Added Ketones Using Pd(II)-NHC Complexes.

机构信息

Department of Chemistry, Faculty of Science, King Abdul-Aziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia.

Department of Chemistry, Faculty of Science, University of Allahabad (AoU), Prayagraj 211002, Uttar Pradesh, India.

出版信息

Molecules. 2023 Jun 25;28(13):4992. doi: 10.3390/molecules28134992.

DOI:10.3390/molecules28134992
PMID:37446653
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10343575/
Abstract

For the creation of adaptable carbonyl compounds in organic synthesis, the oxidation of alcohols is a crucial step. As a sustainable alternative to the harmful traditional oxidation processes, transition-metal catalysts have recently attracted a lot of interest in acceptorless dehydrogenation reactions of alcohols. Here, using well-defined, air-stable palladium(II)-NHC catalysts (A-F), we demonstrate an effective method for the catalytic acceptorless dehydrogenation (CAD) reaction of secondary benzylic alcohols to produce the corresponding ketones and molecular hydrogen (H). Catalytic acceptorless dehydrogenation (CAD) has been successfully used to convert a variety of alcohols, including electron-rich/electron-poor aromatic secondary alcohols, heteroaromatic secondary alcohols, and aliphatic cyclic alcohols, into their corresponding value-added ketones while only releasing molecular hydrogen as a byproduct.

摘要

在有机合成中创造适应性羰基化合物时,醇的氧化是一个关键步骤。作为对传统有害氧化过程的可持续替代方案,过渡金属催化剂最近在醇的无受体脱氢反应中引起了广泛关注。在这里,我们使用定义明确、空气稳定的钯 (II)-NHC 催化剂 (A-F),展示了一种有效方法,可用于催化无受体脱氢 (CAD) 反应,将仲苄醇转化为相应的酮和氢气 (H)。催化无受体脱氢 (CAD) 已成功用于将各种醇(包括富电子/缺电子芳香族仲醇、杂芳族仲醇和脂环醇)转化为相应的有价值的酮,而仅释放氢气作为副产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/da2da263b2a0/molecules-28-04992-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/f1cb6f795edd/molecules-28-04992-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/ee1d6eb81f02/molecules-28-04992-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/d13ef4f06637/molecules-28-04992-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/92487ea6c20c/molecules-28-04992-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/835a5b51491d/molecules-28-04992-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/da2da263b2a0/molecules-28-04992-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/f1cb6f795edd/molecules-28-04992-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/ee1d6eb81f02/molecules-28-04992-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/d13ef4f06637/molecules-28-04992-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/92487ea6c20c/molecules-28-04992-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/835a5b51491d/molecules-28-04992-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d418/10343575/da2da263b2a0/molecules-28-04992-sch004.jpg

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Acceptorless Alcohol Dehydrogenation Catalysed by Pd/C.钯/碳催化的无受体醇脱氢反应。
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Manganese-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols With Sulfones: A Tool To Access Highly Substituted Vinyl Sulfones.锰催化醇与砜的无受体脱氢偶联反应:一种合成高度取代乙烯基砜的方法
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Catalytic Transfer Hydrogenation with a Methandiide-Based Carbene Complex: An Experimental and Computational Study.基于亚甲基卡宾配合物的催化转移氢化:实验与计算研究
Chemistry. 2015 Nov 2;21(45):16103-12. doi: 10.1002/chem.201502116. Epub 2015 Sep 25.
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A molecular iron catalyst for the acceptorless dehydrogenation and hydrogenation of N-heterocycles.一种用于 N-杂环化合物的无受体脱氢和加氢的分子铁催化剂。
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