Towards the 150th Anniversary of the Markovnikov Rule

Abstract

The Markovnikov rule,k nownt oe very student of organic chemistry,w as formulated 150 years ago,i n1 869. During its long history (almost as long as the history of organic chemistry itself), attitudes towards this famous statement of chemical reactivity have evolved from indifference up to the 1930s,t hrough common acceptance as au seful educational paradigm with marginal use in researchu pt ot he 1990s,t oi ts vigorous relauncha sa ni mportant designation of regioselectivity in the last few decades.The unexpected new popularity of the classical rule is accounted for by the rapid expansion in catalytic addition reactions and their critical importance as highly effective atom-economical, regioselective methods in modern organic synthesis.Ah istorical outline of the life and achievements of Vladimir Markovnikov is included to reveal the very wide scope of his interests as well as his prophetic predictions on structure,reactivity,selectivity,stereochemistry, and other key issues of organic chemistry.

Electrochemical Epoxidation of Propylene to Propylene Oxide via Halogen-Mediated Systems

“…For the situation that an elemental halogen as an active species attacks propylene to form halonium ion (path II), a halonium ion intermediate was proposed to be an intermediate species in the electrophilic addition process to alkenes. , The intermediate species attacks the double bond to obtain the halonium ion intermediate, and then, the hydroxyl group is added to the middle carbon atom through nucleophilic attack. The whole process obeyed Markovnikov rules where electrophilic groups will preferentially combine with edge carbons and nucleophilic groups will preferentially combine with intermediate carbons or carbons containing less hydrogen . However, such a reaction path requires a higher energy barrier, which means that the reaction is more difficult to occur.…”

Nikolay Zelinsky (1861–1953): Mendeleev's Protege, a Brilliant Scientist, and the Top Soviet Chemist of the Stalin Era

“…At Moscow University, Zelinsky was the successor to V. Markovnikov (1838–1904) [1,2] . He headed the School of Organic Chemistry at Moscow University for more than 40 years (1893–1938).…”

“…D. Mendeleev and N. Menshutkin played a significant role in this appointment. Zelinsky replaced V. Markovnikov, who had spent years building the highest level chemical school at Moscow University, [2] in this position. He taught the main course in organic chemistry, and practical classes in analytical and organic chemistry.…”

The Logic Behind Markovnikov's Rule: Was It an Inspired Guess? …No!

“…At the same time, Markovnikov used his dissertation to show how this theory was superior to the Type Theory that Kolbe used. He would continue his advocacy after he had graduated as Magistr Khimii , and had embarked on a komandirovka , or official study leave, with Kolbe in Leipzig [3j,k, 12] …”