ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 17276 - 17285
Опубликована: Ноя. 8, 2024
Chiral
polysubstituted
aromatic
γ-butyrolactones
are
core
structural
units
of
many
natural
products
and
high
value-added
chemicals
in
the
pharmaceutical
food
industries.
Currently,
precise
construction
multiple
chiral
centers
on
five-membered
heterocycle
substituted
by
bulky
phenyl
groups
faces
big
challenges,
such
as
low
stereoselectivity,
expensive
noble
metal
catalysts,
harsh
reaction
conditions
atom
economy.
Herein,
we
report
a
one-pot,
two-enzyme
catalytic
strategy
for
synthesis
18
di/trisubstituted
α-,
β-
γ-carbons
with
good
enantioselectivities
(up
to
>99%
ee)
diastereoselectivities
>99:1
dr).
This
cascade
process
includes
sequential
two-step
asymmetric
reduction
α-/β-unsaturated
γ-ketoesters
four
ene
reductases
carbonyl
reductase
without
intermediate
isolation
catalyst
removal.
In
particular,
large
sterically
hindered
substrates
(1p–1s)
were
converted
corresponding
trisubstituted
(4p–4s)
98–99%
ee
dr.
enzymatic
represents
simple,
atom-economic
enantioselective
method
deliver
broad
cheap
efficient
manner
compared
conventional
methods.
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 129 - 138
Опубликована: Дек. 16, 2024
Semiconductor-based
photocatalysis
has
evolved
over
the
past
decade
into
a
prevalent
approach
for
alcohol
oxidation
to
afford
corresponding
carbonyl
compounds
or
C–C/C–O
coupled
products.
Nonetheless,
photocatalytic
oxidative
lactonization
of
diols
lactones
still
significantly
lags
behind,
even
though
represent
class
ring
moieties
with
excellent
biological
activities.
In
this
work,
we
present
high-performance
visible-light-mediated
and
H2
Ti3C2Tx
MXene-supported
CdS
quantum
dots
(QDs)
Ni
decoration
(Ni/CdS/Ti3C2Tx).
acts
as
two-dimensional
platform
immobilizing
promote
separation
migration
charge
carriers,
while
concomitantly
Cd2+
confinement
effect
retards
hole-induced
photocorrosion
CdS.
The
unique
modifications
atomically
dispersed
species
are
either
incorporated
clusters
in
accelerate
evolution,
anchored
single
atom
on
efficient
adsorption
cyclization
diols.
optimized
Ni/CdS/Ti3C2Tx
exhibits
remarkably
enhanced
activity
lactone
synthesis,
which
is
80.4
times
higher
than
that
blank
CdS,
along
selectivity
high
durability.
This
work
brings
conceptual
idea
overcome
well-known
intrinsic
drawback
photoinduced
decomposition
semiconductor-based
photocatalysts
offers
generic
robust
strategy
utilizing
cocatalyst
active
sites
photoredox
synthesis
evolution.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 17, 2024
Abstract
This
review
analyzes
a
development
in
biochemistry,
enzymology
and
biotechnology
that
originally
came
as
surprise.
Following
the
establishment
of
directed
evolution
stereoselective
enzymes
organic
chemistry,
concept
partial
or
complete
deconvolution
selective
multi‐mutational
variants
was
introduced.
Early
experiments
led
to
finding
mutations
can
interact
cooperatively
antagonistically
with
one
another,
not
just
additively.
During
past
decade,
this
phenomenon
shown
be
general.
In
some
studies,
molecular
dynamics
(MD)
quantum
mechanics/molecular
mechanics
(QM/MM)
computations
were
performed
order
shed
light
on
origin
non‐additivity
at
all
stages
an
evolutionary
upward
climb.
Data
used
construct
unique
multi‐dimensional
rugged
fitness
pathway
landscapes,
which
provide
mechanistic
insights
different
from
traditional
landscapes.
Along
related
line,
biochemists
have
long
tested
result
introducing
two
point
enzyme
for
reasons,
followed
by
comparison
respective
double
mutant
so‐called
cycles,
showed
only
additive
effects,
but
more
recently
also
uncovered
cooperative
antagonistic
non‐additive
effects.
We
conclude
suggestions
future
work,
call
unified
overall
picture
epistasis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 24, 2024
Abstract
Repurposing
enzymes
to
catalyze
non‐natural
asymmetric
transformations
that
are
difficult
achieve
using
traditional
chemical
methods
is
of
significant
importance.
Although
radical
C−O
bond
formation
has
emerged
as
a
powerful
approach
for
constructing
oxygen‐containing
compounds,
controlling
the
stereochemistry
poses
great
challenge.
Here
we
present
development
dual
bio‐/photo‐catalytic
system
comprising
an
ene‐reductase
and
organic
dye
achieving
stereoselective
lactonizations.
By
integrating
directed
evolution
photoinduced
single
electron
oxidation,
repurposed
engineered
ene‐reductases
steer
formations
(one
hydrolactonizations
lactonization‐alkylations
while
two
bonds
lactonization‐oxygenations).
This
catalysis
gave
new
diverse
array
enantioenhanced
5‐
6‐membered
lactones
with
vicinal
stereocenters,
part
which
bears
quaternary
stereocenter
(up
99
%
enantiomeric
excess,
up
12.9
:
1
diastereomeric
ratio).
Detailed
mechanistic
studies,
including
computational
simulations,
uncovered
synergistic
effect
enzyme
externally
added
organophotoredox
catalyst
Rh6G.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11004 - 11044
Опубликована: Янв. 1, 2024
This
review
provides
a
mechanistic
overview
of
asymmetric
Fe,
Cu,
Pd,
Rh,
Au
and
heme-based
enzymes
catalyzed
carbene
insertion
reactions
to
construct
C–X
(X
=
O,
N,
S,
etc.
)
C–C
bonds,
focusing
on
the
stereochemical
models.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4984 - 5001
Опубликована: Март 10, 2025
Unprecedented
chiral
ruthenium(II)
complexes
with
phthalocyanines
having
motifs
near
the
catalytic
metal
site
have
been
prepared
by
cross
condensation
of
3,6-bis-aryloxy-phthalonitrile
(α-Ar*O)2Pn
bearing
two
(1R,2S,5R)-menthoxy
groups
orthogonal
to
aromatic
plane
and
(15-crown-5)phthalonitrile.
Four
containing
menthyl
(M)
15-crown-5
units
(C),
notably
RuPc[MC3](CO),
RuPc[opp-M2C2](CO),
RuPc[adj-M2C2](CO),
RuPc[M3C](CO),
were
isolated
in
pure
form
fully
characterized
UV–vis,
circular
dichroism,
HRMS,
various
1H
NMR
13C
techniques.
Their
evaluation
benchmark
asymmetric
cyclopropanation
reaction
styrene
derivatives
ethyl
diazoacetate
indicated
that
RuPc[opp-M2C2](CO)
complex
was
most
efficient
terms
diastereo-
enantioselectivity.
Further
study
revealed
strong
dependence
stereoselectivity
on
solvent
nature
salt
additives,
which
caused
conformational
rearrangement
flexible
surrounding,
as
evidenced
multinuclear
CD
spectra.
For
instance,
upon
moving
from
commonly
used
CH2Cl2
EtOH
addition
NaPF6,
a
significant
enhancement
enantioselectivity
(from
35
84%
p-methylstyrene)
obtained.
Of
particular
importance
is
very
high
diastereoselectivity
many
substrates
promoted
incorporation
sodium
cations
into
crown
ether
cavities
phthalocyanine
attain
trans/cis
ratio
up
499:1.
Such
regulating
effect
catalysis
involving
tetrapyrrolic
has
not
previously
observed,
rendering
this
prominent
example
tunable
catalyst.
The
developed
synthetic
strategy
paves
way
environment
around
receptors
tune
properties.
Cationic
diruthenium
(II,III)
tetracarboxylate
catalysts
have
been
shown
to
catalyze
selective
intermolecular
C-H
functionalization
reactions
using
donor/acceptor
carbenes
in
high
yield
and
with
levels
of
enantioselectivity.
The
were
compared
the
analogous
dirhodium
(II,II)
showed
similar
enantioselectivity
for
most
reactions.
A
distinctive
feature
is
a
greater
preference
over
cyclopropanation
corresponding
catalysts.
Also,
sterically
more
accessible
sites
their
counterparts.
These
studies
show
that
are
generally
effective
enantioselective
functionalization,
but
further
optimization
would
be
needed
them
match
terms
functional
group
compatibility,
turnover
frequency,
numbers.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
this
review,
we
have
showcased
the
diverse
aspects
of
transition-metal
catalysis,
biocatalysis,
and
photocatalytic
C(sp
3
)–H
bond
functionalization
to
access
lactones
lactams.
