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Fringuelli, F.; Piermatti, O., Science of Synthesis: Water in Organic Synthesis, (2012) 1, 485.
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 120 hours 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]
Meeeee 8 Meeeeee Meeeeeeeeeeee “Me Meeee”[88]
Meeeeeeeee | Meeee (%) | Mee |
---|---|---|
eeee | 88 | [88] |
MeMM | 88e | [88] |
“ee eeeee” | 888 | [88] |
e 88% ee 8-eeeeee-8-eeeeeeee eee eeeeeee.
Meeeeeee-eeeee eeeeeeeee eee eeee ee eeeeeee eeeeeeeee ee eeeee eeeeeeeee eeeeeeee eee eeeeeeee eeee eeeee eeeeeee eeeeeeeeee.[88,88] Meee eeee eeeeee ee eee Meeeeee eeeeeeeeeeeee. 8-(Meeeeeee)-8-eeeeeeeeeeeee (88, M8 = Me) ee eeeeeeeeeeeeeee ee 888 °M eeeee ee 88:88 eeeeeee ee eeeee- eee eeee-eeeeeee 88 eee 88 ee 88 eeeee (Meeeee 8).[88] Me eeeeeeeeeeeeeee eee ee eee eeeeeeee ee eeeeeeeeeeeeeeeee, eee eeeeeeee ee eeeeeeee ee 88 eeeee ee eeee eeeeeeeeeee eeeeeee eee eeeeeeeeeee eeeeeeeee ee eee eeeee ee 88/88.[88] Mee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeee ee eeeee eee e eeeeeeeeee eeeeee ee eee eeeeeeee eeee eee eeeeeeeee eee eeeeee ee eeee-Meeeeee eeeeee 88 eeeeee, eeeeee eeee e eeeee eeeeeeeeeee ee eeeeeee (e.e., M8 = eMe, e-Me).
Meeeee 8 Meeeeeeeeeeeeeeee Meeeeee Meeeeeeeeeeeee ee 8-Meeee-8-(eeeeeeee)eeeeeeee ee ee Meeeeee Meeeee[88]
M8 | Meeeeeee | Meee (°M) | Meee (e) | Meeeee (88/88) | Mee |
---|---|---|---|---|---|
Me | –e | ee | 88 | 88:88 | [88] |
Me | M8M | ee | 8 | 88:88 | [88] |
eMe | M8M | ee | 88 | 88:88 | [88] |
e-Me | M8M | −88 | 8 | 88:8 | [88] |
e Me eee eeeee eee eeeeeeeeee eee >88%.
e Me eee eeeeeee ee eeee eeeeeeee eee Me8Me eee eeeeeeee eeeeee ee 888 °M eeeeeeeee 88/88 ee 88:88 eeeee.[88]
Mee eeeeeeeeee eeeeee ee eeeee ee eeee eeeeeeee ee eee eeeeeeee Meeeeee eeeeeeeeeeeeee ee eeeee eeeeee 88 eeee eeee eeeee- eee eeee-eeeeeee 88 eee 88 eeeeeee ee eee eeeeeeeeeee (Meeeee 8).[88]
Meeeee 8 Meeeeeee Meeeeee Meeeeeeeeeeeee ee ee Meeeeee Meeeee[88]
M8 | M8 | M8 | Meeee (%) | Meeee (88/88) | Mee |
---|---|---|---|---|---|
M | Me | Me | 88 | 88:88 | [88] |
Me | Me | Me | 88 | 88:88 | [88] |
Me | Me | M | 88 | 88:88 | [88] |
References
[27] | Meeeeee, M.; Meeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[38] | Meeeeee, M.; Meeeeee, M.; Meee, M. M.; Meeee, M. M.; Meee, M. M.; Meeeeeeee, M. M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[39] | Meeeeeeeee, M.; Meeee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[40] | Meeeeeeeee, M.; Meeee, M.; Meeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[41] | Meeeeee, M. M.; Meeeeeeeee, M.; Meeeeeee, M.; Meeeeeeeee, M. M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[42] | Meee, M.; Meeeíeeee, M., Mee. Meeee. Meeee., (8888) 888, 888. |