Metalloenzymes catalyze a variety of reactions using a limited number of natural amino
acids and metallocofactors. Therefore, the environment beyond the primary coordination …

Discovered as organometallic curiosities in the 1970s, carbene radicals have become a
staple in modern-day homogeneous catalysis. Carbene radicals exhibit nucleophilic radical …

The effective design of combinatorial libraries to balance fitness and diversity facilitates the
engineering of useful enzyme functions, particularly those that are poorly characterized or …

The study of non-natural biocatalytic transformations relies heavily on empirical methods,
such as directed evolution, for identifying improved variants. Although exceptionally …

Chiral amines can be made by insertion of a carbene into an N–H bond using two-catalyst
systems that combine a transition metal-based carbene-transfer catalyst and a chiral proton …

Transition-metal-catalyzed carbene insertion reactions of a nitrogen–hydrogen bond have
emerged as robust and versatile methods for the construction of C–N bonds. While …

The renaissance in corrole chemistry is strongly correlated with synthetic breakthroughs that
started in 1999, regarding the one-pot rather than multistep syntheses of this heme-like N4 …

New-to-nature radical biocatalysis has recently emerged as a powerful strategy to tame
fleeting open-shell intermediates for stereoselective transformations. In 2021, we introduced …

Engineered metalloenzymes represent promising catalysts for stereoselective C–H
functionalization reactions. Recently, P450 enzymes have been evolved to allow for new-to …

Directed evolution has the potential to enable abiological chemistry by engineering natural
enzymes to function on non-natural substrates. In this study, we expanded the repertoire of …