Original author: Li Qiang, School of Chemistry and Chemical Engineering, Liaocheng University, this account is authorized to publish it on behalf of others.
For more than a century, Nobel Prize in Chemistry has been awarded to organic synthesis methodology 7 times in total. These seven awards were all about the synthetic methodology of building carbon-carbon bonds, in which asymmetric reactions involved two. This is not surprising, because the essence of organic synthesis of is how to efficiently, easily and atomically economically connect carbon atoms together. However, the carbon that makes up living organisms is relatively inert, and carbon atoms do not react easily with each other, so connecting carbon chains together is a very difficult thing. Initially, the methods used by organic chemists to link carbon atoms were mostly based on techniques that pre-shelled carbons were more active. These methods are quite efficient when making simple molecules, but often the effect is not ideal when synthesizing more complex bioactive molecules.
Figure 1 Richard Heck (left), Eiichi Nekiki (middle), Akira Suzuki (right)
In the past half century, metal-catalyzed coupling reactions have become one of the most important and common methods for building carbon-carbon bonds, and are widely used in the fields of medicine, electronics industry and advanced materials research. 2010 Nobel Prize in Chemistry was awarded to three chemists who have outstanding contributions in this field. Richard Heike , Eiichi Nekiki and Suzuki Chau. The reason for winning is the "Palladium Catalytic Cross-coupling in Organic Synthesis" study, commending their contributions in the development and use of palladium to prepare carbon-carbon bond compounds.
The palladium catalytic coupling reactions they studied and many similar chemical reactions developed inspired by them have been widely used in academic and industrial fields, with far-reaching impacts. However, most of these reactions use precious metal palladium catalysts. Interestingly, nickel-catalyzed coupling reactions have begun to occur over the past 20 years. Compared with expensive palladium catalysts, nickel catalyst has the advantage of being relatively cheap and rich in content. Because it has the special activity of catalyzing cross-coupling reaction , nickel catalysts exhibit unique catalytic activity for cross-coupling reactions involving electrophiles with low activity under palladium catalytic conditions.
We will naturally ask: Why is it nickel? What makes this metal the best catalyst for the above reaction?
Figure 2 Basic parameters of nickel element
nickel is element No. 28, belonging to Group VIII, and the oxidation valence state can change significantly. It is common in major compounds +2, +3 and +4-valent nickel. Nickel also has good corrosion resistance and plasticity, so it is mainly used in various military manufacturing industries such as steel, nickel-based alloy , civilian machinery manufacturing, plating and battery industries, etc. In addition, it can also become an indispensable catalyst for many chemical reactions. The structure determines properties and can have such catalytic properties because as one of the transition metals of D-region , the ability of nickel to bond with carbon atoms is attributed to nickel itself, the relatively positive electrical properties, and the flexible and variable valence state of nickel, which can form a variety of geometric configurations and form a variety of chemical bonds, including organic metal bonds, . In addition, easier nickel carbon bond rotation avoids β-H to eliminate side reactions.
References:
1. From coins to batteries New energy chemical elements tour: Nickel https://zhuanlan.zhihu.com/p/496902989
2. Different element stories: Nickel, related to survival | "Nature-Chemistry" column https://zhuanlan.zhihu.com/p/67625391
tutor profile
Li Qiang, doctoral, lecturer, master's supervisor. In 2016, he received his PhD in Science from Hunan University and joined the School of Chemistry and Chemical Engineering of Liaocheng University in the same year. In 2021, he was appointed as a master's supervisor. Currently, it is mainly engaged in the study of inert chemical bonds and selective activation and recombination of small molecules, and the construction and transformation of phosphorus chiral centers.As the first or corresponding author, he has published more than ten SCI papers in mainstream academic journals such as Org. Lett., Org. Chem. Front., J. Org. Chem., Org. Biomol. Chem., and presided over the Shandong Provincial Natural Science Foundation and the National Natural Science Foundation Youth Project.
admissions major: Organic chemistry
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-