Welcome to the Named Reactions category, where we explore the significant transformations in organic chemistry that bear the names of renowned chemists. Dive into the rich history and fundamental mechanisms behind reactions such as the Grignard reaction, Diels-Alder reaction, and Heck reaction, among others. Uncover the applications, limitations, and synthetic utility of these named reactions in organic synthesis. Discover how these reactions have shaped the field of organic chemistry and continue to inspire innovation. Embark on a journey through the world of named reactions and unlock the secrets of their chemical transformations.
What is Henkel reaction? The Henkel reaction, which is also referred to as the Raecke process, is an industrial-scale chemical transformation involving the thermal rearrangement or disproportionation of alkaline salts derived from aromatic acids. This process occurs in the presence of metallic salts, such as cadmium, and results in the formation of symmetrical diacids. References … Read more
What is Hofmann-Martius rearrangement? The Hofmann-Martius rearrangement, or aniline rearrangement, which involves the thermal conversion of hydrohalides of N-alkylated aromatic amines to produce o-alkylated and p-alkylated aromatic amine derivatives, was initially documented by Hofmann and Martius in 1871. When N-alkylated aromatic amine hydrochlorides are heated, they dissociate, and the resulting components undergo intermolecular alkylation through … Read more
What is Bradsher cyclization? The Bradsher cyclization, also known as the Bradsher reaction, Bradsher-type aromatic cyclodehydration, and Parham cyclization, was first reported by Bradsher in 1939. This acid-catalyzed cyclization reaction is commonly used for synthesizing various polycyclic aromatic compounds, particularly those in the phenanthrene series. In addition, various functional groups attached to an aromatic ring … Read more
What is Craig 2-bromo-pyridine synthesis? In 1915, Chichibabin and Ryasanjev reported the preparation of 2-bromopyridine from 2-aminopyridine, but the yield was low. Later, in 1934, Craig reported a modified method for producing high yields of 2-bromo-pyridine (α-position) from 2-amino-pyridine. As a result, this reaction is commonly referred to as the Craig 2-bromo-pyridine synthesis or Craig … Read more
What is Duff reaction? The Duff reaction, also known as the Duff formylation or Duff synthesis, was reported by Duff and Bills in 1932. It involves the formylation of phenols or aromatic amines in a mixture of hexamethylenetetramine (HMT), boric acid H3BO3, and glycerol (see list of acronyms). The Duff reaction typically proceeds very quickly and … Read more
What is Gewald reaction? In 1965, Gewald reported a reaction that involves a base-catalyzed condensation of a ketone with α-ketonitrile to produce an olefin that cyclizes with sulfur and is useful for synthesizing 2-aminothiophene. This reaction is known as the Gewald reaction and has various names such as Gewald synthesis of 2-aminothiophene, or Gewald aminothiophene … Read more
What is Boyland-Sims oxidation? The Boyland-Sims Oxidation, also referred to as the Boyland-Sims peroxydisulfate oxidation, was initially discovered by Boyland and Sims in 1953. This particular oxidation reaction converts primary, secondary, and tertiary aromatic amines to o-sulfate esters, which are then further transformed into the corresponding alcohols. The Boyland-Sims Oxidation is a two-step process that … Read more
What is Bradsher cycloaddition? The Bradsher cycloaddition involves a [4+2] cycloaddition reaction that occurs between a commonly used dienophile and cationic aromatic azadienes such as acridizinium or isoquinolinium. References C.K. Bradsher, T.W.G. Solomons, “Acridizinium Ion Chemistry. II. The Diels-Alder Reaction” Journal of the American Chemical Society 1958 80 (4), 933-934 DOI: 10.1021/ja01537a045
What is Nazarov cyclization? Nazarov cyclization is an organic chemical reaction in which a compound with a conjugated enone and a terminal alkene is converted into a cyclohexenone through the action of an acid catalyst. The reaction was discovered by the Russian chemist Pyotr Nazarov in the 1950s and is named after him.. Nazarov cyclization … Read more
What is Kumada cross coupling? Kumada cross-coupling is a chemical reaction used in organic synthesis to synthesize new organic compounds. It involves the coupling of two organic molecules using a transition metal catalyst, typically nickel, palladium, or cobalt. The reaction was first reported in 1964 by Masatoshi Kumada, hence the name.. In the Kumada cross-coupling … Read more
