In their analysis of experiments and in their planning of syntheses, organic
chemists consciously or unconsciously tend to use the principle of least motion,
the chemical equivalent ofOccam’s razor. In rearrangement reactions this principle
is violated and may make rearrangements problematic reactions. At the
same time, there is always fascination in the unexpected and so rearrangement
reactions are also an attractive field of study. Consequently, our understanding
of rearrangement reactions is now quite advanced and allows strategic uses
in organic synthesis. Here, a helpful tool that may easily be overlooked is
the influence of organosulfur functionalities on these rearrangements. In fact,
the presence of sulfur may make rearrangements predictable and productive
or allow specific transformations which would otherwise require a tedious
synthetic detour. The present account is meant to spread this knowledge. In
addition, an introductory chapter gives a survey of the basics of organosulfur
chemistry to put the information in the individual chapters into perspective
and to help readers who are less familiar with the peculiarities of sulfur in an
organic environment.