Water-accelerated organic transformations

Chemical Communications Pub Date: 2001-01-30 DOI: 10.1039/B008252J

Abstract

Rather than quenching all reactive intermediates and arresting the reaction, the addition of catalytic or stoichiometric (1–10 equiv.) quantities of H2O to organic and organometallic processes can lead to surprisingly beneficial effects on reaction rate, product yield, and regio-, diastereo- and enantioselectivity. A most intriguing aspect of H2O-promoted transformations is the role that this strong Lewis-base can play in providing a source for more highly Lewis-acidic species. This scenario is most likely operative when H2O is added to reaction mixtures containing alanes, but organozinc reagents or organocuprates also seem to be transformed accordingly. In addition, the oxide or hydroxide ligand on the metal presents a source for chelation interactions that change aggregation states of organometallics and can provide anchimeric assistance. In many cases, water has been found to be an effective hydrolyzing agent leading to secondary products that serve as catalysts or promoters. In some cases, it has been shown that water provides a quenching agent capable of driving chemical equilibria towards the desired products.

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