Chemical Science,
Год журнала:
2022,
Номер
13(45), С. 13611 - 13616
Опубликована: Янв. 1, 2022
Sulfoximines
are
synthetically
important
scaffolds
and
serve
roles
in
drug
discovery.
Currently,
there
is
no
solution
to
decarboxylative
sulfoximination
of
benzoic
acids;
although
thoroughly
investigated,
limited
substrate
scope
harsh
reaction
conditions
still
hold
back
traditional
thermal
aromatic
functionalization.
Herein,
we
realize
the
first
acids
via
photo-induced
ligand
copper
charge
transfer
(copper-LMCT)-enabled
carbometalation.
The
transformation
proceeds
under
mild
conditions,
has
a
broad
scope,
can
be
applied
late-stage
functionalization
complex
small
molecules.
Accounts of Chemical Research,
Год журнала:
2023,
Номер
56(9), С. 1057 - 1069
Опубликована: Апрель 12, 2023
ConspectusAs
a
renewable
solar
energy
and
carbon
carrier,
biomass
exploration
has
received
global
attention.
Photocatalytic
valorization
of
into
fuels
chemicals
is
promising
sustainable
method
for
future
chemical
production.
Photocatalysis
the
potential
to
accomplish
reactions
under
ambient
conditions
due
unique
reaction
mechanisms
involving
photoinduced
charge
carriers
recently
been
recognized
as
an
efficient
feasible
technology
conversion.
Biomass
widely
used
sacrificial
agent
scavenge
holes
in
photocatalytic
hydrogen
evolution,
eventually
degraded
CO2
with
minor
amount
CO.
The
generation
CO
instead
more
economical
but
also
challenge
photoreforming
conditions.This
new
research
direction,
while
until
now
there
still
lack
comprehensive
review
article
summarize
provide
prospects
this
topic.
This
Account
will
highlight
our
contributions
direction
reforming
syngas
(CO
+
H2).
In
2020,
we
first
reported
conversion
biopolyols
sugars
by
employing
defect-rich
Cu-TiO2
nanorod
photocatalyst
found
that
formic
acid
key
intermediate
Further
study
revealed
facet-dependent
electron-trapping
state
on
anatase
TiO2
affect
dehydration
activity
intermediates
regulating
electron
transfer
process
during
reaction,
selective
FA
or
from
was
achieved
via
exposing
(100)
(101)
facets,
respectively.
Visible
light-driven
further
over
CdS-based
photocatalyst.
Sulfate
modification
CdS
([SO4]/CdS)
constructed
proton
acceptor,
thus
efficiently
facilitating
proton-coupled
process.
Besides,
put
forward
oxygen-controlled
strategy
increase
rate
without
significant
decrease
selectivity
controlling
O2/substrate
ratio.
Based
system,
Z-scheme
CdS@g-C3N4
core-shell
structure
CdO-CdS
semicoherent
interface
were
created
facilitate
enhance
O2
activation,
increasing
rate.
Moreover,
developed
photoelectrochemical
approach
separately
produce
H2
biomass.
Nitrogen
doping
hexagonal
WO3
nanowire
array
photoanode.
built-in
electric
field
generated
nitrogen
promoted
transfer,
hence
improving
efficiency
PEC
sugars.
systematically
analyze
challenges
route
reforming,
factors
affecting
give
insight
design
systems.
Science,
Год журнала:
2023,
Номер
382(6669), С. 458 - 464
Опубликована: Окт. 26, 2023
Stereochemical
enrichment
of
a
racemic
mixture
by
deracemization
must
overcome
unfavorable
entropic
effects
as
well
the
principle
microscopic
reversibility;
recently,
photochemical
reaction
pathways
unveiled
energetic
input
light
have
led
to
innovations
toward
this
end,
most
often
ablation
stereogenic
C(sp3)-H
bond.
We
report
photochemically
driven
protocol
in
which
single
chiral
catalyst
two
mechanistically
different
steps,
C-C
bond
cleavage
and
formation,
achieve
multiplicative
enhancement
stereoinduction,
leads
high
levels
stereoselectivity.
Ligand-to-metal
charge
transfer
excitation
titanium
coordinated
phosphoric
acid
or
bisoxazoline
efficiently
enriches
alcohols
that
feature
adjacent
fully
substituted
centers
enantiomeric
ratios
up
99:1.
Mechanistic
investigations
support
pathway
sequential
radical-mediated
scission
formation
through
common
prochiral
intermediate
reveal
that,
although
overall
stereoenrichment
is
high,
selectivity
each
individual
step
moderate.
ACS Catalysis,
Год журнала:
2023,
Номер
13(13), С. 8731 - 8751
Опубликована: Июнь 16, 2023
Electrochemically
driven
hydrogen
atom
transfer
(HAT)
catalysis
provides
a
complementary
approach
for
the
transformation
of
redox-inactive
substrates
that
would
be
inaccessible
to
conventional
electron
(ET)
catalysis.
Moreover,
electrochemically
HAT
could
promote
organic
transformations
with
either
abstraction
or
donation
as
key
step.
It
versatile
and
effective
tool
direct
functionalization
C(sp3)–H/Si–H
bonds
hydrofunctionalization
alkenes.
Despite
these
attractive
properties,
has
been
largely
overlooked
due
lack
understanding
both
catalytic
mechanism
how
catalyst
selection
should
occur.
In
this
Review,
we
give
an
overview
applications
in
The
mechanistic
pathways,
physical
properties
mediators,
state-of-the-art
examples
are
described
discussed.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(10), С. 1538 - 1564
Опубликована: Март 6, 2023
Abstract
Quaternary
pyridinium
compounds
are
valuable
intermediates
in
organic
synthesis,
which
have
gained
immense
popularity
the
synthetic
community.
The
application
of
transition
metal
or
photoredox
catalysis
transforming
quaternary
into
various
C−C
and
C−X
bonds
is
well
established.
A
majority
these
methods
require
high
temperatures,
expansive
catalysts,
delicate
conditions
for
successful
execution.
On
other
hand,
use
metal‐free
photocatalysis‐free
strategies
constructing
using
derivatives
has
been
sought‐after.
In
this
context,
electron‐donor‐acceptor
(EDA)‐complex
reactions
emerged
as
a
state‐of‐the‐art
methodology,
do
not
any
photocatalyst
their
EDA‐complex
photochemistry
takes
advantage
electron‐acceptor
ability
derivatives,
can
quickly
generate
radical
precursor
via
deaminative
process.
These
newly
generated
useful
several
transformations.
We
hereby,
review,
discuss
an
area
major
progress
mediated
involving
with
mechanism,
substrate
scope,
limitations.
magnified
image
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 3861 - 3868
Опубликована: Фев. 9, 2023
A
visible-light
photoredox-catalyzed
method
is
reported
that
enables
the
coupling
between
benzylic
C-H
substrates
and
N-H
azoles.
Classically,
medicinally
relevant
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2748 - 2756
Опубликована: Янв. 12, 2024
Controlling
the
enantioselectivity
of
hydrogen
atom
transfer
(HAT)
reactions
has
been
a
long-standing
synthetic
challenge.
While
recent
advances
on
photoenzymatic
catalysis
have
demonstrated
great
potential
non-natural
photoenzymes,
all
transformations
are
initiated
by
single-electron
reduction
substrate,
with
only
one
notable
exception.
Herein,
we
report
an
oxidation-initiated
enantioselective
hydrosulfonylation
olefins
using
novel
mutant
gluconobacter
ene-reductase
(GluER-W100F-W342F).
Compared
to
known
systems,
our
approach
does
not
rely
formation
electron
donor–acceptor
complex
between
substrates
and
enzyme
cofactor
simplifies
reaction
system
obviating
addition
regeneration
mixture.
More
importantly,
GluER
variant
exhibits
high
reactivity
broad
substrate
scope.
Mechanistic
studies
support
proposed
mechanism
reveal
that
tyrosine-mediated
HAT
process
is
involved.
Chemical Reviews,
Год журнала:
2024,
Номер
124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(5), С. 2326 - 2349
Опубликована: Янв. 1, 2024
This
review
summarizes
the
advances
in
metal-catalyzed
asymmetric
reactions
enabled
by
organic
peroxides
that
have
been
found
to
exhibit
multifunctionalities,
for
instance,
applied
as
stoichiometric
reactants,
reagents,
or
catalytic
amount
reagents.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
The
integration
of
ligand-to-metal
charge
transfer
(LMCT)
catalytic
paradigms
with
radical
intermediates
has
transformed
the
selective
functionalization
inert
C-H
bonds,
facilitating
use
nonprecious
metal
catalysts
in
demanding
transformations.
Notably,
aerobic
carbonylation
methane
to
acetic
acid
remains
formidable
due
rapid
oxidation
methyl
radicals,
producing
undesired
C1
oxygenates.
We
present
an
iron
terpyridine
catalyst
utilizing
LMCT
achieve
exceptional
C2/C1
selectivity
through
synergistic
photoexcitation,
generation,
and
carbonylation.
Mechanistic
studies
highlight
critical
roles
Fe(II)
Fe-carbonyl
complexes
bypassing
via
a
rebound-like
pathway,
unlocking
unprecedented
efficiency
