While investigating the intramolecular Schmidt reaction, we used pi–cation and n–cation interactions in the context of controlling sterochemistry and regiochemistry. Although these interactions are common features in small molecule–protein interactions, they are rarely used in chemical synthesis. In addition, our group discovered a class of intriguing twisted amides in which the amide bond is somewhere between totally planar and totally orthogonal. These new agents have been used in a variety of reactions including mild and selective C–C activation reactions. The intramolecular Schmidt reaction has been applied to stereo- and regio- chemically controlled ring expansions in order to introduce a nitrogen-containing group in a complex molecular setting. The lab also continues to exploit the unique properties of fluorinated alcohols, such as hexafluoroisopropanol (HFIP), to promote unusual reactivity, as shown in recent rearrangements and Friedel-Crafts substitution chemistry.