6 research outputs found
Developing a Biocascade Process: Concurrent Ketone Reduction-Nitrile Hydrolysis of 2‑Oxocycloalkanecarbonitriles
A stereoselective
bioreduction of 2-oxocycloalkanecarbonitriles was concurrently coupled
to a whole cell-catalyzed nitrile hydrolysis in one-pot. The first
step, mediated by ketoreductases, involved a dynamic reductive kinetic
resolution, which led to 2-hydroxycycloalkanenitriles in very high
enantio- and diastereomeric ratios. Then, the simultaneous exposure
to nitrile hydratase and amidase from whole cells of <i>Rhodococcus
rhodochrous</i> provided the corresponding 2-hydroxycycloalkanecarboxylic
acids with excellent overall yield and optical purity for the all-enzymatic
cascade
From oximes to tertiary alcohols in water, at room temperature and under air: a hybrid one-pot tandem assembly of enzymatic deoximation and RLi/RMgX reagents
: The highly efficient biodeoximation of aromatic ketoximes, promoted by the enzymatic oxidative system laccase/TEMPO/O2, has been successfully assembled with the fast and chemoselective addition of highly-polar s-block organometallic reagents (RLi/RMgX) en route to highly-substituted tertiary alcohols. By using this hybrid one-pot tandem protocol, tertiary alcohols have been selectively synthesized in good yields and under mild and bench-type reaction conditions (room temperature, the absence of a protecting atmosphere and aqueous media, which are non-typical conditions for polar organometallic reagents). The overall hybrid one-pot tandem transformation amalgamates two distant organic synthetic tools (RLi/RMgX reagents and enzymes) without the need for any tedious and energy/time-consuming intermediate isolation/purification steps
Stereoselective Chemoenzymatic Synthesis of Enantiopure 2‑(1<i>H</i>‑imidazol-yl)cycloalkanols under Continuous Flow Conditions
The development of continuous flow processes for the
synthesis
of chiral enantiopure 1-(2-hydroxycycloalkyl)imidazoles is reported.
For the ring-opening reaction microwave batch processes and continuous
flow reactions have led to similar results in terms of conversion,
although the productivity is clearly improved under flow. The use
of continuous flow systems for the lipase-catalyzed kinetic resolution
of the racemic 2-(1<i>H</i>-imidazol-yl)cycloalkanols with
either immobilized CAL-B or PSL-C has been demonstrated to be significantly
more efficient than the corresponding batch processes. The continuous
flow biotransformations have allowed us to easily increase the production
of these chiral imidazoles, adequate building blocks in the synthesis
of chiral ionic liquids
Combination of Metal-Catalyzed Cycloisomerizations and Biocatalysis in Aqueous Media: Asymmetric Construction of Chiral Alcohols, Lactones, and γ‑Hydroxy-Carbonyl Compounds
The
combination of the metal-catalyzed cycloisomerization of alkynes
containing a tethered nucleophile as substituent in aqueous media
(followed by the spontaneous hydrolysis, hydroalkoxylation, or aminolysis
of the transiently formed five-membered heterocycles) with the subsequent
enantioselective ketone bioreduction (mediated by KREDs) has been
achieved. The overall transformations, which formally involve a three-step
one-pot reaction, provide a variety of enantiopure valuable molecules
(e.g., 1,4-diols, lactones, and γ-hydroxy-carbonyl compounds
(carboxylic acids, esters, and amides)) with high conversions and
enantioselectivities and under mild reaction conditions, disclosing
the concept of integrated metal-catalyzed cycloisomerizations of alkynes
and enzymatic catalysis in water