Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(44)
Published: Sept. 14, 2023
Abstract
The
regioselectivity
of
C−H
functionalization
is
commonly
achieved
by
directing
groups,
electronic
factors,
or
steric
hindrance,
which
facilitate
the
identification
reaction
sites.
However,
such
strategies
are
less
effective
for
reactants
as
simple
monofluoroarenes
due
to
their
relatively
low
reactivity
and
modest
demands
fluorine
atom.
Herein,
we
present
an
undirected
gold‐catalyzed
para
‐C−H
arylation
a
wide
array
using
air‐stable
aryl
silanes
germanes
at
room
temperature.
A
high
‐regioselectivity
(up
98
:
2)
can
be
realized
utilizing
dinuclear
dppm(AuOTs)
2
(dppm=bis(diphenylphosphino)methane)
catalyst
hexafluorobenzene
solvent.
This
provides
general
practical
protocol
concise
construction
structurally
diverse
‐arylated
through
activation
manner.
It
features
excellent
functional
group
tolerance
broad
substrate
scope
(>80
examples).
Besides,
this
strategy
also
robust
other
monosubstituted
arenes
heteroarenes.
Our
mechanistic
studies
theoretical
calculations
suggest
that
selectivity
arises
from
highly
electrophilic
flexible
Ar−Au(III)−Au(I)
species,
coupled
with
noncovalent
interaction
induced
hexafluorobenzene.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 1635 - 1654
Published: Jan. 15, 2025
Metallaphotoredox
cross
coupling
(MCC)
is
ranking
among
the
most
advanced
synthetic
methodology
as
it
can
access
chemical
space
that
difficult
to
attain
under
conventional
conditions.
Earlier
developed
MCC
mandates
an
independent
transition
metal
catalyst
and
respective
photocatalyst,
thus
constituting
a
dual
catalytic
manifold.
Complementarily,
paradigm-shifting
metallaphotoredox
strategy
capitalizes
on
single
photoreactive
complex
emerging,
which
brings
not
only
operational
simplification
but
also
unexpected
mechanistic
insights.
This
perspective
compiled
recent
advances
in
monocatalytic
couplings
categorized
them
based
ligands
confer
distinct
photoreactivities
various
mechanisms.
To
this
end,
ligand-enabled
oxidative
addition,
transmetalation,
reductive
elimination
other
radical-involving
pathways
were
summarized
with
notable
examples.
In
way,
we
wish
provide
handy
guideline
for
readers
who
are
interested
emerging
field
inspire
more
future
endeavors
MCCs
beyond.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Dec. 14, 2023
Selective
defluorinative
functionalization
of
trifluoromethyl
group
(-CF3)
is
an
attractive
synthetic
route
to
the
pharmaceutically
privileged
fluorine-containing
moiety.
Herein,
we
report
a
strategy
based
on
photoexcited
copper
catalysis
activate
C-F
bond
di-
or
trifluoromethylated
arenes
for
divergent
radical
C-N
coupling
with
carbazoles
and
aromatic
amines.
The
use
different
ligands
can
tune
reaction
products
diversity.
A
range
substituted,
structurally
diverse
α,α-difluoromethylamines
be
obtained
from
via
carbazoles,
while
interesting
double
ready
difluoromethylated
arenes.
Based
this
success,
carbazole-centered
PNP
ligand
designed
optimal
ligand,
enabling
copper-catalyzed
construction
imidoyl
fluorides
amines
through
functionalization.
Interestingly,
1,2-difluoroalkylamination
styrenes
also
developed,
delivering
γ,γ-difluoroalkylamines,
bioisostere
β-aminoketones,
in
synthetically
useful
yields.
DFT
studies
reveal
inner-sphere
electron
transfer
mechanism
Cu-catalyzed
selective
activation
C(sp3)-F
bonds.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 2, 2024
The
enormous
and
widespread
use
of
organoboronic
acids
has
prompted
the
development
innovative
synthetic
methodologies
to
meet
demands
on
structural
diversity
functional
group
tolerance.
existing
photoinduced
defunctionalization
radical
borylation,
typically
focused
conversion
one
C-X
bond
(X=
Br,
I,
or
other
leaving
group)
into
only
C-B
bond.
Herein,
we
disclose
a
divergent
dechloroborylation
reaction
enabled
by
dinuclear
gold
catalysis
with
visible
light
irradiation.
A
wide
range
structurally
diverse
alkyl
boronic,
α-chloroboronic,
gem-diboronic
esters
can
be
synthesized
in
moderate
good
yields
(up
92%).
Its
robustness
is
further
demonstrated
preparative
scale
applied
late-stage
diversification
complex
molecules.
process
hinges
C-Cl
relay
activation
readily
available
gem-dichloroalkanes
through
inner-sphere
electron
transfer,
overcoming
redox
potential
limits
unreactive
chlorides.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(49), P. 26756 - 26764
Published: Dec. 1, 2023
The
classical
Au(I)/Au(III)
redox
couple
chemistry
has
been
limited
to
constructing
C–C
and
C–X
bonds,
thus,
the
exploration
of
elementary
reaction
gold
coupling
is
very
significant
enrich
its
organometallic
features.
Herein,
we
report
first
visible-light-mediated,
external
oxidant-free
using
commercially
available
Mn2(CO)10
generate
Mn–Au(III)–Mn
intermediates
for
bimetallic
coupling.
A
wide
range
structurally
diverse
heterodinuclear
polynuclear
L–Au(I)–Mn–L′
complexes
(19
examples,
up
>99%
yields)
are
readily
constructed,
providing
a
robust
strategy
concise
construction
Au–Mn
under
mild
conditions.
mechanistic
studies
together
with
DFT
calculations
support
radical
oxidative
addition
•Mn(CO)5
reductive
elimination
mechanisms
from
highly
active
species,
representing
an
important
step
toward
in
research.
Furthermore,
resulting
exhibit
unique
catalytic
activity,
which
divergent
nitroarenes
can
afford
azoxybenzenes,
azobenzenes,
hydrazobenzenes
moderate
good
yields.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(4), P. 2238 - 2246
Published: Jan. 31, 2024
Visible-light-induced
regioselective
cascade
radical
cyclization
of
α-bromocarbonyls
for
the
synthesis
benzazepine
derivatives
is
described.
In
presence
fac-Ir(ppy)3
(2.0
mol
%)
as
a
photocatalyst,
2,6-lutidine
base,
and
dichloromethane
solvent,
reactions
proceed
smoothly
to
afford
seven-membered
rings
in
good
yields.
This
protocol
features
broad
substrate
scope,
excellent
functional
group
tolerance,
mild
reaction
conditions.
Preliminary
mechanistic
studies
reveal
that
generation
α-carbon
more
prone
react
with
1,1-diphenylethylene
tethered
acrylamide
generate
stable
heterocycle.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(44)
Published: Sept. 14, 2023
The
regioselectivity
of
C-H
functionalization
is
commonly
achieved
by
directing
groups,
electronic
factors,
or
steric
hindrance,
which
facilitate
the
identification
reaction
sites.
However,
such
strategies
are
less
effective
for
reactants
as
simple
monofluoroarenes
due
to
their
relatively
low
reactivity
and
modest
demands
fluorine
atom.
Herein,
we
present
an
undirected
gold-catalyzed
para-C-H
arylation
a
wide
array
using
air-stable
aryl
silanes
germanes
at
room
temperature.
A
high
para-regioselectivity
(up
98
:
2)
can
be
realized
utilizing
dinuclear
dppm(AuOTs)2
(dppm=bis(diphenylphosphino)methane)
catalyst
hexafluorobenzene
solvent.
This
provides
general
practical
protocol
concise
construction
structurally
diverse
para-arylated
through
activation
manner.
It
features
excellent
functional
group
tolerance
broad
substrate
scope
(>80
examples).
Besides,
this
strategy
also
robust
other
monosubstituted
arenes
heteroarenes.
Our
mechanistic
studies
theoretical
calculations
suggest
that
selectivity
arises
from
highly
electrophilic
flexible
Ar-Au(III)-Au(I)
species,
coupled
with
noncovalent
interaction
induced
hexafluorobenzene.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(12), P. 3391 - 3396
Published: Jan. 1, 2024
An
efficient
electrochemical
oxidation
of
ω-azido
carboxylic
acids
followed
by
an
intramolecular
Schmidt
reaction
for
synthesis
1-pyrroline
has
been
reported.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(22), P. 5705 - 5709
Published: Jan. 1, 2023
A
gold-catalyzed
Si–H
bond
insertion
reaction
of
1,6-enynes
with
hydrosilanes
via
cyclopropyl
gold
carbene
intermediates
is
herein
reported,
and
a
into
Ge–H
bonds
reported
for
the
first
time.
Synthesis,
Journal Year:
2023,
Volume and Issue:
56(11), P. 1711 - 1718
Published: Oct. 31, 2023
Abstract
A
photoredox-catalyzed
protocol
for
performing
radical
difunctionalization
of
alkenes
using
N-heterocyclic
carbene
(NHC)
boranes
and
alkynyl
bromines
is
described.
The
alkynylborylation
reaction
involves
photoredox
generation
boryl
radical,
with
subsequent
addition
to
the
double
bond
followed
by
capture
bromide
form
a
C–C
bond.
This
method
features
mild
conditions,
remarkable
chemoselectivity,
broad
substrate
scope
good
excellent
yields
(up
89%).
modification
coumarin
derivatives
indicates
that
this
approach
can
provide
useful
route
synthesis
complex
alkynylborylated
products.