Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

Abstract

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.

Unveiling the origin of the chemoselectivity of bismacycle-mediated C–H arylation of phenols: from mechanism concept to new coupling design

“…Finally, these predicted low barriers for the designed substrates may promote and enhance further synthetic approaches in the area of bismacycle Bi(V)/Bi(III). 57,58…”

A Highly Efficient Bismuth Nitrate/Keto-ABNO Catalyst System for Aerobic Oxidation of Alcohols to Carbonyl Compounds under Mild Conditions

“…Bismuth, as a non-toxic, cheap, and readily available metal, has been applied as a suitable ecofriendly reagent in cosmetic and medicinal chemistry. Moreover, due to the non-toxicity and inexpensive characteristics of bismuth and its compounds, they are also used as efficient catalysts for many organic reactions [23][24][25][26][27][28]. Recently, our group employed bismuth(III) salts as a highly efficient co-catalyst for the direct oxidative esterification of alcohols [29].…”

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

“…The environmentally benign nature of bismuth compounds offers access to novel sustainable materials and led to developments, e.g., in catalysis, medicine, radiopaque additives, and electronics [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ]. Among the starting materials used for the synthesis of solid-state materials, bismuth(III) nitrate pentahydrate is one of the most common and readily available compounds.…”