ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(18), P. 11152 - 11158
Published: Aug. 31, 2022
The
Cr-catalyzed
Nozaki–Hiyama–Kishi
reaction
serves
as
a
reliable
and
valuable
C–C
bond
construction
strategy
in
organic
synthesis.
However,
known
asymmetric
transformations
are
limited
mainly
to
primary
Cr
intermediates
with
an
α-substituted
π-functional
group,
which
impeded
their
further
synthetic
applications.
Herein,
we
described
three-component
reaction,
provides
modular
access
chiral
β-hydroxy
sulfides
selenides
vicinal
stereocenters.
Based
on
preliminary
mechanistic
studies,
this
method
proceeds
via
the
reductive
radical-polar
crossover,
featuring
unprecedented
secondary
alkyl
complex
stabilized
by
α-sulfur
or
selenium.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(7), P. 4742 - 4751
Published: March 23, 2023
Methionine
sulfoxide
reductase
A
(MsrA)
enzymes
have
recently
found
applications
as
nonoxidative
biocatalysts
in
the
enantioselective
kinetic
resolution
of
racemic
sulfoxides.
This
work
describes
identification
selective
and
robust
MsrA
able
to
catalyze
reduction
a
variety
aromatic
aliphatic
chiral
sulfoxides
at
8-64
mM
concentration
with
high
yields
excellent
ees
(up
99%).
Moreover,
aim
expand
substrate
scope
biocatalysts,
library
mutant
has
been
designed
via
rational
mutagenesis
utilizing
silico
docking,
molecular
dynamics,
structural
nuclear
magnetic
resonance
(NMR)
studies.
The
enzyme
MsrA33
was
bulky
substrates
bearing
non-methyl
substituents
on
sulfur
atom
up
99%,
overcoming
significant
limitation
currently
available
biocatalysts.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 2, 2025
Enzymes
are
attractive
catalysts
due
to
their
high
chemo-,
regio-,
and
enantioselectivity.
In
recent
years,
the
application
of
enzymes
in
organic
synthesis
has
expanded
dramatically,
especially
for
chiral
alcohols
amines,
two
very
important
functional
groups
found
many
active
pharmaceutical
ingredients
(APIs).
Indeed,
elegant
routes
employing
such
compounds
have
been
described
by
industry.
Yet,
thiols
thioethers,
likewise
APIs
albeit
less
ubiquitous,
only
few
biocatalytic
syntheses
reported,
stereocontrol
proved
challenging.
Here,
we
apply
ene-reductases
(EREDs),
whose
ability
initiate
control
chemically
challenging
radical
chemistries
recently
emerged,
thioethers
from
α-bromoacetophenones
pro-chiral
vinyl
sulfides,
without
requiring
light.
Depending
on
choice
ERED
either
enantiomer
product
could
be
accessed.
The
highest
conversion
selectivity
were
achieved
with
GluER
T36A
using
fluorinated
substrates,
reaching
up
82%
>99.5%
ee.
With
α-bromoacetophenone
α-(methylthio)styrene,
reaction
performed
a
100
mg
scale,
affording
46%
isolated
yield
93%
Finally,
mechanistic
studies
carried
out
stopped-flow
spectroscopy
protein
mass
spectrometry,
providing
insight
into
preference
enzyme
intermolecular
reaction.
This
work
paves
way
new
thioether-containing
compounds.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
metal-free
protocol
for
the
modular
synthesis
of
diverse
α-thiofunctionalized-α′-carbonyl
sulfoxonium
ylides
from
sulfoxonium–iodonium
hybrid
(I
(III)
/S
(VI)
-ylides)
has
been
achieved.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(13), P. 9287 - 9297
Published: June 19, 2024
A
copper-catalyzed
three-component
coupling
reaction
of
styrene
oxide,
aryl
iodide,
and
carbon
disulfide
for
the
construction
β-hydroxysulfides
has
been
developed.
In
this
process,
readily
available
CS2
was
used
as
sulfur
source
to
construct
C–S
bonds
synthesis
phenyl-β-hydroxysulfides
(benzo[d]thiazol)-β-hydroxysulfides.
This
process
features
mild
conditions,
simple
operation,
wide
substrate
scope
(>50
examples).
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(36), P. 9863 - 9871
Published: Jan. 1, 2023
Designing
an
alternative
access
to
the
morphinan
scaffold
by
taking
advantage
of
biocatalysis
for
asymmetric
CN
reduction
and
oxidative
C–C
bond
formation.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(3), P. 1465 - 1472
Published: Jan. 22, 2024
Enzyme-catalyzed
dynamic
kinetic
resolution
was
applied
to
the
one-pot
regio-
and
enantioselective
synthesis
of
2,5-disubstituted
tetrazole
hemiaminal
esters,
among
which
72%
products
were
obtained
in
excellent
enantiopurities
(99%
ees).
Tunable
stereoselectivity
achieved
by
using
different
types
enzymes
during
a
key
intermediate
for
clinic
drug
candidate.
Successful
preparation
ester
prodrugs
high
catalyst
recyclability
further
demonstrated
potential
practical
application
this
protocol.
