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5.2.1.1.3 Rearrangement of Allyl Aryl Ethers

DOI: 10.1055/sos-SD-206-00325

Fringuelli, F.; Piermatti, O.Science of Synthesis: Water in Organic Synthesis, (20121485.

A procedure used for highly water-insoluble reagents is to submit an aqueous suspension of reagents to strong stirring, which increases the area of surface contact between the molecules, accelerating the reaction (on water protocol).[‌38‌] An example is illustrated in Scheme 6. The Claisen rearrangement of highly water-insoluble 4-chloro-1-naphthol derivative 26 to 27 is complete in 120hours at 23°C by using the on water procedure while a lower conversion and byproducts are obtained working at the same temperature under neat conditions or in methanol under homogeneous conditions.[‌38‌] The origin of the on water effect has been investigated theoretically using QM/MM Monte Carlo calculations and the free-energy perturbation theory.[‌27‌]

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