For reasons of economy and pollution, solvent-free methods are of great int
erest in order to modernize classical procedures making them more clean, sa
fe and easy to perform. Reactions on solid mineral supports, reactions with
out any solvent/support or catalyst, and solid-liquid phase transfer cataly
sis can be thus employed with noticeable increases in reactivity and select
ivity. A comprehensive review of these techniques is presented here. These
methodologies can moreover be improved to take advantage of microwave activ
ation as a beneficial alternative to conventional heating under safe and ef
ficient conditions with large enhancements in yields and savings in time.