Baeyer–Villiger Monooxygenases: Tunable Oxidative Biocatalysts

Pollution,
accidents, and misinformation have earned the pharmaceutical
and chemical industry a poor public reputation, despite their undisputable
importance to society. Biotechnological advances hold the promise
to enable a future of drastically reduced environmental impact and
rigorously more efficient production routes at the same time. This
is exemplified in the Baeyer–Villiger reaction, which offers
a simple synthetic route to oxidize ketones to esters, but application
is hampered by the requirement of hazardous and dangerous reagents.
As an attractive alternative, flavin-containing Baeyer–Villiger
monooxygenases (BVMOs) have been investigated for their potential
as biocatalysts for a long time, and many variants have been characterized.
After a general look at the state of biotechnology, we here summarize
the literature on biochemical characterizations, mechanistic and structural
investigations, as well as enzyme engineering efforts in BVMOs. With
a focus on recent developments, we critically outline the advances
toward tuning these enzymes suitable for industrial applications.