The advent of new catalysts greatly contributes to improving efficiency in organic synthesis. In the last decades, all sorts of metal and organic catalysts have been investigated thoroughly toward this end. Nevertheless, there are some catalytic functionalities based on main group elements which remain untapped due to the difficulty in harnessing their very low or uncontrollably high reactivity. Our goal is to turn these catalytic functionalities into valuable synthetic tools, especially for enantioselective synthesis, by molecular design. We have succeeded in developing catalysts using carboxylic acid, boronic acid, thiyl radical and electrophilic selenium, respectively, and controlling a variety of polar and radical transformations unique to their catalytic properties. In this presentation, I will introduce a few topics from these studies including the latest advances.