Bismuth has recently been shown to be able to maneuver between different oxidation states, enabling access to unique redox cycles that can be harnessed in the context of organic synthesis. Indeed, various catalytic Bi redox platforms have been discovered and revealed emerging opportunities in the field of main group redox catalysis. The goal of this perspective is to provide an overview of the synthetic methodologies that have been developed to date, which capitalize on the Bi redox cycling. Recent catalytic methods via low-valent Bi(II)/Bi(III), Bi(I)/Bi(III), and high-valent Bi(III)/Bi(V) redox couples are covered as well as their underlying mechanisms and key intermediates. In addition, we illustrate different design strategies stabilizing low-valent and high-valent bismuth species, and highlight the characteristic reactivity of bismuth complexes, compared to the lighter p-block and d-block elements. Although it is not redox catalysis in nature, we also discuss a recent example of non-Lewis acid, redox-neutral Bi(III) catalysis proceeding through catalytic organometallic steps. We close by discussing opportunities and future directions in this emerging field of catalysis. We hope that this Perspective will provide synthetic chemists with guiding principles for the future development of catalytic transformations employing bismuth.
© 2022 The Authors. Published by American Chemical Society.