Sulfinylamines (R-N=S=O), monoaza analogues of sulfur
dioxide, have been known for well over a century, and their reactivity
as sulfur electrophiles and in Diels-Alder reactions is well-established.
However, they have only rarely been used in organic synthesis in
recent decades despite the increasing prominence of compounds
containing N=S=O functionality, such as sulfoximines and
sulfonimidamides. This Minireview aims to bring wider visibility to the
unique chemistry enabled by this class of compounds. We focus on
advances from the last 10 years, including the first examples of their
use in the one-pot syntheses of sulfoximines and sulfonimidamides.
Also covered are the reactions of sulfinylamines with carbon-centered
radicals, their use for the formation of heterocycles through
cycloadditions, and catalytic enantioselective allylic oxidation of
alkenes via a hetero-ene reaction. These examples highlight the
different reactivity modes of sulfinylamines and their
underappreciated potential for forming molecules which contain highor
low-valent sulfur, or even no sulfur at all.
