Robby Vroemans

The advancement in Ni-catalyzed C−S bond formation reactions are summarized in this review and literature is covered from 2015–2021. In organic chemistry, C−S bond formation reactions play an eminent role, due to its wide applicability in various fields. Ni-catalyzed C−S bond formation has captured tremendous attractiveness due to its easy accessibility, low cost and comparatively low toxicity. The mechanisms of some of the reactions are also added, giving perception into the synthetic and the mechanistic details of its chemistry.

Abstract

Recently, sulphur containing molecules have witnessed significant recognition due to their wide application in various fields. In this regard, the synthesis of such C−S containing moieties has become a distinguished and omnipresent research sector in organic chemistry. The transition metal catalysts have been widely utilized in this field for the C−S bond formation. Among them, nickel catalysts have attracted great attention owing to their relatively lower toxicity, highly economical, plentiful and efficient metal which come up as a substitute for toxic and expensive 4d and 5d transition metals. The latest advancement in nickel-catalyzed C−S bond making reactions are reviewed and covers literature from 2015–2021.

The origins of organic chemistry and organic synthesis started in the middle ages, long before molecular compositions were known. Paradigm shifts caused by Lavoisier, Chevreuil, Wöhler, Liebig, Kolbe and Berthelot are highlighted. The graphic shows some early key organic molecules, but although synthesis and analysis had become well established sciences by the 1840s, the chemical structures remained essentially unknown.

Abstract

The words organic and synthesis originate with Aristotle (meaning ‘instrumental’ and ‘put together’, respectively) but had different meanings over time. The iatrochemists prepared numerous pharmaceutical remedies in the 1600s but had no concept of organic chemistry. Buffon, Bergman and Gren defined organic bodies as living things in the 1700s, but discrete organic compounds remained unknown. In the late 1700s and early 1800s, organic natural products were isolated by Scheele, and Chevreuil separated carboxylic acids from saponification of fats. Organic chemistry had started. Lavoisier invented and Berzelius improved combustion analysis for organic characterization. Descartes’ dictum that synthesis is required to prove an analysis was enacted by Bergman and others. The concept of organic chemistry changed radically when Wöhler and Kolbe prepared organic compounds from the elements. Berthelot's syntheses of non-natural fats in 1853 started modern synthetic organic chemistry as the chemistry of carbon compounds, regardless of whether occurring in Nature or not.

A Ni(0)-catalyzed methodology efficiently achieves C_sp2−OMe functionalization in the presence of internal alkynes, forming chemoselectively either aromatic homologation or intramolecular monoannulation products. Furthermore, aromatic homologation products are proven as valid precursors for further diversification towards nanographene-like synthesis.

Abstract

A Ni-catalyzed C_sp2−OMe ortho-functionalization methodology to form chemoselectively alkyne monoannulation or aromatic homologation products is reported as a novel protocol towards the valorisation of substrates containing C_sp2−OMe units. Double activation of C_sp2−OMe and C_sp2−F bonds is also demonstrated. Further use of aromatic homologation products towards the synthesis of nanographene-like compounds is described.

Copper- and nickel-catalyzed cross-coupling reactions of different electrophiles and nucleophiles or two types of nucleophiles are alternative synthetic procedures to palladium-based processes to access functional organic molecules and heterocycles. A variety of carbon-carbon and carbon-heteroatom bonds could be synthesized via recently developed protocols under microwave irradiation conditions. The focus of this review article is accentuated on the recent development and sustainable achievement performed during the last ten years.

Abstract

The use of transition metals in cross-coupling reactions has been verified as a powerful tool in synthetic organic chemistry to access valuable pharmaceutical intermediates and functional organic molecules. Copper compounds were described for building a variety of Carbon-Carbon and Carbon-Heteroatom bonds more than a century ago. Whereas nickel-catalyzed cross-coupling was emerged in the 1972. The general reactivity of the reaction conversion was enhanced during the last two decades, particularly under microwave irradiation conditions. The focus of this review article accentuates the recent development and sustainable achievement of copper- and nickel-catalyzed cross-coupling of different electrophiles and nucleophiles or two sort of nucleophiles under microwave irradiation conditions. The published cross-coupling protocols during the last ten years were critically reviewed, this includes the type and amount of metal catalyst used, solventless and ligandless conditions and the application in the synthesis of complex heterocycles. Furthermore, various proposed reaction mechanisms covering radical path or through the involvement of metal complexes in different oxidation states were highlighted and discussed.

Kenichi Fukui was the first Japanese chemist to receive the Nobel Prize. Fukui shared the 1981 Nobel Prize in Chemistry with Roald Hoffmann “for their theories, developed independently, concerning the course of chemical reactions.” This paper discusses Fukui, the person.

Abstract

Kenichi Fukui shared the 1981 Nobel Prize in Chemistry with Roald Hoffmann for “their theories, developed independently, concerning the course of chemical reactions.” This is Paper 4 – Part I, of a three-part trilogy within a 27-paper series on the history of the development of the Woodward-Hoffmann rules. The personality and professional style of Fukui is discussed as well as his style of teaching and his mottos and sayings. A brief chronological history of his academic and professional life is presented along with a listing of Fukui's great flexibility in behaviors and in science. Lastly, a short list of Fukui's key awards is provided.

Synthesis
DOI: 10.1055/s-0041-1737909

Hypervalent iodine (HVI) reagents have gained much attention as versatile oxidants because of their low toxicity, mild reactivity, easy handling, and availability. Despite their unique reactivity and other advantageous properties, stoichiometric HVI reagents are associated with the disadvantage of generating non-recyclable iodoarenes as waste/co-products. To overcome these drawbacks, the syntheses and utilization of various recyclable hypervalent iodine reagents have been established in recent years. This review summarizes the development of various recyclable non-polymeric, polymer-supported, ionic-liquid-supported, and metal–organic framework (MOF)-hybridized HVI reagents.1 Introduction2 Polymer-Supported Hypervalent Iodine Reagents2.1 Polymer-Supported Hypervalent Iodine(III) Reagents2.2 Polymer-Supported Hypervalent Iodine(V) Reagents3 Non-Polymeric Recyclable Hypervalent Iodine Reagents3.1 Non-Polymeric Recyclable Hypervalent Iodine(III) Reagents3.2 Recyclable Non-Polymeric Hypervalent Iodine(V) Reagents3.3 Fluorous Hypervalent Iodine Reagents4 Ionic-Liquid/Ion-Supported Hypervalent Iodine Reagents5 Metal–Organic Framework (MOF)-Hybridized Hypervalent Iodine Reagents6 Conclusion
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“Single-atom catalysts are like a magic box…” This and more about the story behind the research that inspired the Cover image is presented in the Cover Profile. Read the full text of the corresponding research at 10.1002/cssc.202102494. View the Front Cover here: 10.1002/cssc.202200357.

Abstract

Invited for this month′s cover is the group of Haifeng Xiong at Xiamen University. The image shows that single-atom catalysts can work in the catalytic oxidation of volatile organic compounds. The Review itself is available at 10.1002/cssc.202102494.

Nature Chemistry, Published online: 17 March 2022; doi:10.1038/s41557-022-00898-0

Nature Catalysis, Published online: 17 March 2022; doi:10.1038/s41929-022-00744-z