Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(9), С. 1009 - 1031
Опубликована: Дек. 8, 2023
Comprehensive
Summary
Construction
of
C—F
bonds
is
a
direct
and
efficient
method
for
introducing
fluorine
into
pharmaceuticals,
agrochemicals,
materials.
Strategies
such
as
nucleophilic,
electrophilic,
radical,
transition‐metal
catalyzed
fluorination
have
been
developed
to
meet
the
demand
diverse
bond
formation.
Among
them,
radical
has
witnessed
with
substantial
advancement
in
recent
decade.
Herein,
we
reviewed
methods
formation
carbon‐centered
radicals
key
intermediates,
especially
five
years.
We
introduce
paper
different
fluorinating
reagents,
strategies
generation,
application
late‐stage
functionalization
synthesis
PET
tracers.
also
indicate
current
limitations
propose
direction
field
future
development.
Key
Scientists
Radical
was
recognized
an
old
uncontrolled
reaction
that
may
date
back
time
when
element
first
mixed
organic
compounds
by
Henri
Moissan
1891.
The
development
slow
combination
discovery
new
reagents.
Substantial
changes
took
place
2012,
example
carbon
robust
mild
NFSI
Selectfluor,
reported
Sammis
group.
In
same
year,
Groves,
Lectka,
Li,
Boger
led
pioneering
works
on
aliphatic
C—H
fluorination,
decarboxylative
fluorofunctionalization
alkenes
manner.
Photoredox
catalysis
introduced
2013
Chen
group,
which
opens
up
avenue
fluorinative
transformations.
Most
previous
focus
form
C(sp
3
)–F
bonds.
2018,
challenging
non‐directed
aromatic
solved
Ritter
coworkers.
Direct
arene
fluoride
ion
later
disclosed
Nicewicz
group
2019.
There
are
many
other
scientists
made
tremendous
contribution
too
limited
space
list
them
all.
only
those
discoveries
point
fluorination.
Chemical Reviews,
Год журнала:
2023,
Номер
123(8), С. 4237 - 4352
Опубликована: Янв. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(18), С. 9928 - 9950
Опубликована: Апрель 24, 2023
This
Perspective
surveys
the
progress
and
current
limitations
of
nucleophilic
fluorination
methodologies.
Despite
long
rich
history
C(sp3)–F
bond
construction
in
chemical
research,
inherent
challenges
associated
with
this
transformation
have
largely
constrained
to
a
privileged
reaction
platform.
In
recent
years,
Doyle
group─along
many
others─has
pursued
study
development
intent
generating
deeper
mechanistic
understanding,
developing
user-friendly
reagents,
contributing
invention
synthetic
methods
capable
enabling
radiofluorination.
Studies
from
our
laboratory
are
discussed
along
developments
others
field.
Fluoride
reagent
implications
identity
highlighted.
We
also
outline
space
inaccessible
by
technologies
series
future
directions
field
that
can
potentially
fill
existing
dark
spaces.
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:
2023,
Номер
145(33), С. 18487 - 18496
Опубликована: Авг. 11, 2023
We
report
a
visible-light
photoredox-catalyzed
method
that
enables
nucleophilic
amination
of
primary
and
secondary
benzylic
C(sp3)-H
bonds.
A
novel
amidyl
radical
precursor
organic
photocatalyst
operate
in
tandem
to
transform
bonds
into
carbocations
via
sequential
hydrogen
atom
transfer
(HAT)
oxidative
radical-polar
crossover.
The
resulting
carbocation
can
be
intercepted
by
variety
N-centered
nucleophiles,
including
nitriles
(Ritter
reaction),
amides,
carbamates,
sulfonamides,
azoles,
for
the
construction
pharmaceutically
relevant
C(sp3)-N
under
unified
reaction
conditions.
Mechanistic
studies
indicate
HAT
is
radical-mediated
operates
reductive
quenching
pathway.
These
findings
establish
mild,
metal-free,
modular
protocol
rapid
diversification
library
aminated
products.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Фев. 1, 2023
A
method
for
direct
access
to
enantioenriched
benzylic
amides
and
carbamate-protected
primary
benzylamines
by
C-H
functionalization
is
reported.
The
substrate
used
as
limiting
reagent
with
only
a
small
excess
of
the
unactivated
amide
or
carbamate
nucleophile.
enantioselective
intermolecular
dehydrogenative
C-N
bond
formation
enabled
combination
chiral
copper
catalyst,
photocatalyst,
an
oxidant,
it
takes
place
under
mild
conditions,
which
allow
broad
scope.
compatible
late-stage
functionalization,
provides
easy
15
N-labeled
amines
starting
from
cheap
NH4
Cl.
Molecules,
Год журнала:
2023,
Номер
28(16), С. 6127 - 6127
Опубликована: Авг. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts
Chem Catalysis,
Год журнала:
2023,
Номер
3(1), С. 100491 - 100491
Опубликована: Янв. 1, 2023
We
report
the
systematic
development
of
an
electrooxidative
methodology
that
translates
stoichiometric
C–H
fluorination
reactivity
isolable
CuIII
fluoride
complex
into
a
catalytic
process.
The
critical
challenges
electrocatalysis
with
highly
reactive
species
are
addressed
by
judicious
selection
electrolyte,
F−
source,
and
sacrificial
electron
acceptor.
Catalyst-controlled
occurs
preference
for
hydridic
bonds
high
bond-dissociation
energies
over
weaker
but
less
bonds.
selectivity
is
driven
oxidative
asynchronous
proton-coupled
transfer
(PCET)
at
electrophilic
CuIII–F
complex.
further
demonstrate
asynchronicity
factor
hydrogen-atom
transfer,
η,
can
be
used
as
guideline
to
rationalize
fluorination.
Green Chemistry,
Год журнала:
2022,
Номер
24(10), С. 4004 - 4011
Опубликована: Янв. 1, 2022
A
regio-
and
stereoselective
C(sp
2
)–C(sp
3
)
coupling
of
enamides
with
ethers
or
alkanes
via
photoredox-catalyzed
cross-dehydrogenative
reactions
is
developed
under
environmentally
friendly
conditions.
ACS Catalysis,
Год журнала:
2022,
Номер
12(21), С. 13732 - 13740
Опубликована: Окт. 26, 2022
We
introduce
here
a
two-component
annulation
strategy
that
provides
access
to
diverse
collection
of
five-
and
six-membered
saturated
heterocycles
from
aryl
alkenes
family
redox-active
radical
precursors
bearing
tethered
nucleophiles.
This
transformation
is
mediated
by
combination
an
Ir(III)
photocatalyst
Brønsted
acid
under
visible-light
irradiation.
A
reductive
proton-coupled
electron
transfer
generates
reactive
which
undergoes
addition
alkene.
Then,
oxidative
radical-polar
crossover
step
leading
carbocation
formation
followed
ring
closure
through
cyclization
the
nucleophile.
wide
range
are
easily
accessible,
including
pyrrolidines,
piperidines,
tetrahydrofurans,
morpholines,
δ-valerolactones,
dioxanones.
demonstrate
scope
this
approach
broad
structural
variation
both
reaction
components.
method
amenable
gram-scale
preparation
complex
fragment
coupling.