A photoenzymatic NADH regeneration system was established. The combination of deazariboflavin as a photocatalyst with putidaredoxin reductase enabled the selective reduction of NAD+ into the enzyme‐active 1,4‐NADH to promote an alcohol dehydrogenase catalysed stereospecific reduction reaction. The catalytic turnover of all the reaction components was demonstrated. Factors influencing the efficiency of the overall system were identified.
The scale-up of chemoenzymatic
bromolactonization to 100 g scale
is presented, together with an identification of current limitations.
The preparative-scale reaction also allowed for meaningful mass balances
identifying current bottlenecks of the chemoenzymatic reaction.
Biocatalytic pathways
for the synthesis of (−)-menthol,
the most sold flavor worldwide, are highly sought-after. To access
the key intermediate (
R
)-citronellal used in current
major industrial production routes, we established a one-pot bienzymatic
cascade from inexpensive geraniol, overcoming the problematic biocatalytic
reduction of the mixture of (
E/Z
)-isomers in citral
by harnessing a copper radical oxidase (
Cgr
AlcOx)
and an old yellow enzyme (OYE). The cascade using OYE2 delivered 95.1%
conversion to (
R
)-citronellal with 95.9%
ee
, a 62 mg scale-up affording high yield and similar optical
purity. An alternative OYE, GluER, gave (
S
)-citronellal
from geraniol with 95.3% conversion and 99.2%
ee
.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.