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Master Organic Chemistry Reaction Guide

Oxymercuration of Alkenes to form Ethers using Hg(OAc)2

Description: When an alkene is treated with an alcohol in the presence of mercuric acetate [Hg(OAc)2] it will add to the more substituted position of the alkene (Markovnikoff) to give an ether. The mercury can then be removed using NaBH4.

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Real-Life Example:
Org. Synth. 1940, 20, 81
DOI Link: 10.15227/orgsyn.020.0081

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11 thoughts on “Oxymercuration of Alkenes to form Ethers using Hg(OAc)2

    1. Great question!

      It’s adjacent to an electron-withdrawing ketone. Normally you would expect the more substituted carbon to be the best at stabilizing positive charge, but the electron-withdrawing influence of the ketone means that it is in fact the less substituted carbon that is better at stabilizing positive charge.

      Similar “anti-Markovnikov” selectivity is observed in addition to alkenes where one side has a CF3 group or other electron-withdrawing groups.

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