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2.3.2 Addition of Water to C=C Bonds

DOI: 10.1055/sos-SD-215-00136

Resch, V.; Hanefeld, U.Science of Synthesis: Biocatalysis in Organic Synthesis, (20152261.

General Introduction

The addition of water to C=C bonds is a highly interesting reaction in organic chemistry; however, only a few methods for addition to isolated or conjugated C=C bonds have been reported.[‌1‌‌4‌] The number of reports on chemical processes for the large-scale production of alcohols via a water-addition step are very low. Indeed, there is only one industrially employed direct process for the production of tert-butyl alcohol and similar alcohols.[‌5‌] Chemical methods are in general acid catalyzed, including the use of ion-exchange resins {for more information on acid-catalyzed hydration see Science of Synthesis, Vol. 36 [Alcohols (Section 36.1.4.2)]}. Direct chemical hydration is performed for the industrial preparation of ethanol from ethene, isopropyl alcohol from propene, and tert-butyl alcohol from isobutene. These processes suffer from incomplete conversion, and, since the reaction is taking place in the gas phase, expensive gas recycling is necessary to capture unconverted raw material.[‌6‌] In particular, the asymmetric addition of water seems to be a difficult task to achieve by classical chemical means. On the other hand, the use of water as a nucleophile and a solvent at the same time represents an elegant, green, and highly atom-efficient way to access a variety of secondary and tertiary alcohols.[‌7‌] Electronegativity and charge are two very important properties influencing nucleophilicity. In comparison to carbon or nitrogen nucleophiles, water is considered to be a bad nucleophile. Because nucleophilicity increases with the electron density of an atom, water, as an uncharged nucleophile, also shows significantly lower nucleophilicity than charged nucleophiles. Its charged counterpart (OH) displays higher nucleophilicity, but is still less activated in comparison to charged carbon and nitrogen nucleophiles (order: CH3 > NH2 > OH > F). Within the class of oxygen-containing nucleophiles, hydrogen peroxide and its charged species (HOO) are also known to be better nucleophiles than water. Nevertheless, due to its abundance, water serves as a very important and often-employed nucleophile in nature. In enzyme catalysis, sufficient activation is provided and active-site geometry and cofactors allow the correct coordination for hydration reactions to proceed. Furthermore, enzymes are able to bind both the nucleophile and the electrophile and therefore stabilize the transition state,[‌8‌,‌9‌] such that what is essentially an intramolecular reaction takes place. In general, the addition of water is an equilibrium reaction. Even though water is present in excess, the equilibrium is usually not on the product side, and this leads to limitations in the maximum yield achievable. However, this equilibrium strongly depends on the substrate used.

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References


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