Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: April 4, 2025
In
recent
years,
amination
of
alkylboronates
through
ionic
copper
catalysis
or
boron-ate
complex
1,2-metalation
has
been
well
established,
but
complementary
radical
processes
remain
less
studied
before.
Herein,
based
on
rational
design,
we
develop
several
imine-type
N-centered
scavengers
and
apply
them
to
the
alkylboronates.
The
reaction
proceeds
under
mild
photoredox-catalyzed
transition-metal-free
conditions
features
excellent
functional
group
tolerance.
It
also
enables
preparation
a
range
medicinally
valuable
amine
derivatives
from
natural
products.
Further
application
this
reagent
in
C-H
amination,
deoxygenative
decarboxylative
three
component
trifluoromethylative/sulfonylative
aminations
are
realized.
mechanistic
studies
DFT
calculations
conducted
provide
detailed
evidence
for
mechanism.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(3), P. 1300 - 1310
Published: Jan. 11, 2024
Directly
utilizing
abundant
and
inexpensive
sources
of
aliphatic
carboxylic
acids
is
highly
attractive
for
the
synthesis
CF2H-
CH3-containing
compounds.
Herein,
we
report
a
versatile
photoinduced
iron-catalyzed
platform
hydrodifluoromethylation
hydromethylation
alkenes
without
need
additional
stoichiometric
oxidants.
These
two
transformations
are
accomplished
by
visible-light-induced
ligand-to-iron
charge
transfer
open-shell
activation
system
using
industrial
chemical
difluoroacetic
acetic
as
precursors
postulated
to
operate
via
difluoromethyl
methyl
radical-mediated
decarboxylation
mechanism.
Experimental
results
show
that
strategy
also
applicable
difunctionalization
unactivated
alkenes.
Meanwhile,
this
provides
viable
route
pharmaceutically
active
molecules
containing
deuterated
units.
The
protocol
exhibits
several
features,
including
mild
reaction
conditions,
divergent
radical
precursors,
operational
simplicity
scalability,
good
chemo-
regioselectivity,
scalability
supported
continuous
flow
technology,
ability
provide
high-value
building
blocks
applications
in
one
step.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10899 - 10907
Published: April 3, 2024
In
the
long-standing
quest
to
synthesize
fundamental
building
blocks
with
key
functional
group
motifs,
photochemistry
in
recent
past
has
comprehensively
established
its
attractiveness.
Amino
alcohols
are
not
only
functionally
diverse
but
ubiquitous
biologically
active
realm
of
compounds.
We
developed
bench-stable
bifunctional
reagents
that
could
then
access
sparsely
reported
γ-amino
directly
from
feedstock
alkenes
through
energy
transfer
(EnT)
photocatalysis.
A
designed
1,3-linkage
across
is
made
possible
by
intervention
a
radical
Brook
rearrangement
takes
place
downstream
EnT-mediated
homolysis
our
reagent(s).
combination
experimental
mechanistic
investigations
and
detailed
computational
studies
(DFT)
indicates
chain
propagated
reaction
pathway.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5122 - 5129
Published: Jan. 1, 2024
This
study
demonstrates
a
strategy
involving
photoinduced
energy
transfer
for
decarboxylative
Minisci
C–H
(amino)alkylation
of
heteroarenes
employing
diverse
oxime
esters
(from
carboxylic
acids)
as
(amino)alkylating
reagents.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
We
describe
an
efficient
acyl
esterification
method
for
alkenes
utilizing
acyloxime
esters
as
bifunctional
reagents
featuring
radical
acylation
and
congested
C–O
bond
formation.
This
approach
is
characterized
by
mild
photoredox
conditions,
high
step
atom
economy,
a
broad
substrate
scope,
excellent
regioselectivity.
A
variety
of
valuable
α-acyl
hindered
alcohol
esters,
including
those
obtained
via
gram-scale
synthesis
late-stage
functionalization
pharmaceutical
molecules,
were
presented,
demonstrating
its
synthetic
potential
practicability.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(43), P. 23814 - 23823
Published: Oct. 18, 2023
Radical
remote
1,n-difunctionalization
reactions
(n
>
2)
of
alkenes
are
powerful
tools
to
efficiently
introduce
functional
groups
with
selected
distances
into
target
molecules.
Among
these
reactions,
1,5-difunctionalizations
an
important
subclass,
leading
sought-after
scaffolds,
but
typically
suffer
from
tailored
starting
materials
and
strict
limitations
for
the
formed
group
in
2-position.
Seeking
address
issues
make
radical
more
applicable,
we
report
a
novel
three-component
1,2,5-trifunctionalization
reaction
between
imine-based
bifunctional
reagents
two
distinct
alkenes,
driven
by
visible
light
energy
transfer-catalysis.
Key
achieving
this
selective
one-step
installation
three
different
via
choreographed
formation
four
bonds
was
utilization
1,2-boron
shift
rigorous
capitalization
polarities
stabilities.
Thorough
mechanistic
studies
were
carried
out,
synthetic
utility
obtained
products
demonstrated
various
downstream
modifications.
Notably,
addition
functionalization
individual
groups,
their
interplay
gave
rise
unique
array
cyclic
products.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2381 - 2386
Published: March 15, 2024
Organic
sulfones
are
an
important
class
of
chemical
compounds
widely
used
in
many
research
fields.
The
direct
decarboxylative
sulfonylation
carboxylic
acids
is
attractive
but
challenging,
particularly
when
iron
as
a
metal
catalyst.
Herein,
we
describe
photoinduced
iron-catalytic
method
for
the
synthesis
directly
using
via
radical-based
decarboxylation.
This
protocol
mild,
highly
efficient,
and
easy-to-operate.
A
broad
scope
carbon
electrophiles
could
be
well
tolerated.
mechanism
involving
iron-catalyzed
decarboxylation,
radical
transfer,
single-electron
reduction,
nucleophilic
attack
proposed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(3), P. 713 - 718
Published: Jan. 12, 2024
Sulfonamides
are
important
structures
in
pharmaceuticals,
agrochemicals,
and
organocatalysts,
yet
the
rapid
benign
synthesis
of
these
compounds
is
still
a
great
challenge.
Herein
we
report
photoinduced
method
for
synthesizing
sulfonamides
from
(hetero)aryl
carboxylic
acid
oxime
esters.
This
reaction
proceeds
via
one-pot
cascade
radical–radical
cross-coupling
by
energy-transfer-mediated
photocatalysis.
A
wide
substrate
scope
including
substrates
late-stage
modification
pharmaceutical
molecular
entities
reveal
its
generality.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(12), P. 6600 - 6624
Published: Jan. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
