Artificial
metalloenzymes
(ArMs)
have
emerged
as
a
promising
avenue
in
the
field
of
biocatalysis,
offering
new
reactivity.
However,
their
design
remains
challenging
due
to
limited
understanding
protein
dynamics
and
how
introduced
cofactors
alter
scaffold
structure.
Here
we
present
structures
catalytic
activity
novel
copper
ArMs
capable
(R)-
or
(S)-stereoselective
control,
utilizing
steroid
carrier
(SCP)
scaffold.
To
incorporate
2,2’-Bipyridine
(Bpy)
into
SCP,
two
distinct
strategies
were
employed:
either
Bpy
was
an
unnatural
amino
acid
(2,2’-bipyridin-5-yl)alanine
(BpyAla)
using
amber
stop
codon
expression
via
bioconjugation
bromomethyl-Bpy
cysteine
residues.
The
resulting
proved
be
effective
at
catalysing
enantioselective
Friedel-Crafts
reaction
with
SCP_Q111BpyAla
achieving
best
selectivity
enantioselectivity
72%
ee
(S).
Interestingly,
despite
same
scaffold,
different
attachment
for
residue
(Q111)
led
switch
enantiopreference
ArM.
Artificial
metalloenzymes
(ArMs)
have
emerged
as
a
promising
avenue
in
the
field
of
biocatalysis,
offering
new
reactivity.
However,
their
design
remains
challenging
due
to
limited
understanding
protein
dynamics
and
how
introduced
cofactors
alter
scaffold
structure.
Here
we
present
structures
catalytic
activity
novel
copper
ArMs
capable
(
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(32)
Published: April 4, 2024
Abstract
Highly
regioselective
C−H
alkylation
reactions
of
tertiary
anilines
and
alkyl
amines
with
simple
alkenes
have
been
achieved
by
the
use
imidazolin‐2‐iminato
scandium
complexes.
This
protocol
provided
an
efficient
atom‐economical
route
to
structurally
diverse
amine
derivatives.
The
basic
ligand,
a
coordinating
THF
in
catalyst
substitution
alkene
substrates
were
found
switch
regioselectivity
presumably
due
generation
different
types
catalytically
active
species
or
formation
relatively
stable
intermediates.
On
basis
deuterium
labeling
experiments
KIE
experiments,
possible
catalytical
cycles
understand
reaction
mechanism
as
well
regioselectivity.
Nanoscale Advances,
Journal Year:
2024,
Volume and Issue:
6(12), P. 3158 - 3168
Published: Jan. 1, 2024
In
this
research,
a
heterogeneous
acid
catalyst
was
synthesized
by
room
temperature
encapsulation
of
phosphomolybdic
(PMA)
in
the
pores
MIL-53
(Fe)
metal
organic
framework
(MOF)
under
ultrasonic
conditions.
Abstract
A
chiral
Brønsted
acid‐catalyzed
synthesis
of
axially
alkenes
was
developed
via
an
enantioselective
and
para
‐selective
Friedel–Crafts
reaction
between
phenols
1‐alkynylnaphth‐2‐ols.
This
methodology
features
efficient
hydroarylation
with
high
functional
group
tolerance,
complete
‐selectivity,
excellent
yields
(up
to
99%),
enantioselectivities
94%
ee)
in
the
presence
a
N
‐triflylphosphoramide
catalyst.
DFT
calculations
were
performed
investigate
‐selectivity
results
indicate
that
both
kinetics
thermodynamics
parameters
are
more
favorable
compared
ortho
‐selectivity.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
Yoshihara,
Hiroki,
Yagi,
and
Itami
utilized
an
unusual
Friedel-Crafts-like
alkylation
in
the
synthesis
of
adamantane-annulated
arene.
The
precursor
was
a
3°
carbocation,
which
they
proposed
undergoes
Wagner-Meerwein
shift
to
2°
subsequently
alkylates
benzene
ring.
This
mechanism
supported
by
their
DFT
calculations.
However,
choice
B3LYP
functional
often
finds
false
transition
structures.
A
more
appropriate
showed
that
occurs
via
concerted
reaction.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1670 - 1706
Published: Feb. 29, 2024
Abstract
The
Friedel‐Crafts
reaction
stands
as
a
powerful
synthetic
tool
for
C−H
functionalization
of
aromatic
feedstocks,
which
is
conventionally
realized
through
electrophilic
alkylation
and
acylation.
burgeoning
interests
in
axially
chiral
compounds
across
diverse
fields
have
spurred
extensive
exploration
this
classic
transformation
catalytic
atroposelective
synthesis.
Consequently,
the
past
decade
has
witnessed
rapid
expansion
various
non‐canonical
reactions,
including
arylation,
alkenylation,
halogenation,
sulfenylation,
amination
aryl
bonds,
thereby
delving
into
new
chemical
spaces.
A
range
methods
been
devised
these
significant
arene
functionalization.
This
review
provides
comprehensive
overview
cutting‐edge
synthesis
atropoisomers
categorized
three
parts
based
on
type
bond
formation
aromatics:
C(
sp
2
)−C(
3
)
formations,
formations
)−heteroatom
formations.
richness
electrophiles
modulation
atroposelectivity
by
organocatalysts,
particularly
Brønsted
acids,
are
elucidated.
We
anticipate
that
repertoire
asymmetric
will
continue
to
flourish
be
demonstrated
not
only
scientific
researches
but
also
industrial
organic
