Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(33), P. 23555 - 23565
Published: Aug. 8, 2024
Copper-catalyzed
coupling
reactions
of
alkyl
halides
are
believed
to
prominently
involve
copper(II)
species
and
radicals
as
pivotal
intermediates,
with
their
exact
interaction
mechanism
being
the
subject
considerable
debate.
In
this
study,
a
visible
light-responsive
fluoroalkylcopper(III)
complex,
[(terpy)Cu(CF3)2(CH2CO2tBu)]
Trans-1,
was
designed
explore
mechanism.
Upon
exposure
blue
LED
irradiation,
Trans-1
undergoes
copper–carbon
bond
homolysis,
generating
Cu(II)
carbon-centered
radicals,
where
radical
then
recombines
intermediate,
resulting
in
formation
Cis-1,
Cis
isomer
Trans-1.
Beyond
this,
well-defined
fluoroalkylcopper(II)
intermediate
ligated
sterically
hindered
ligand
isolated
underwent
full
characterization
electronic
structure
studies.
The
collective
experimental,
computational,
spectroscopic
findings
work
strongly
suggest
that
organocopper(II)
engages
via
an
"oxidative
substitution"
mechanism,
which
is
likely
operational
pathway
for
copper-catalyzed
C–H
trifluoromethylation
reactions.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 13, 2025
A
visible-light-mediated
photoredox
catalysis
for
β-C(sp3)–H
alkylation
of
1-(o-iodoaryl)alkan-1-ones
with
alkenes
via
1,5-hydrogen
atom
transfer
and
alkene
alkylarylation
to
produce
diverse
β-alkyl
arylalkanones
containing
a
quaternary
carbon
center
is
presented.
This
method
applicable
wide
range
activated
alkenes.
Mechanistic
studies
suggest
that
the
reaction
involves
radical
process.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(39), P. 16050 - 16058
Published: Jan. 1, 2024
We
have
synthesized
β-diaryl-β-hydroxyl-α-amino
acid
derivatives
through
radical
addition-type
aldol
reaction,
which
was
confirmed
by
spectroscopic
experiments,
control
and
DFT
calculations.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
Dual
photoredox
and
copper-catalyzed
remote
asymmetric
C(sp)3-H
alkylation
of
hydroxamic
acid
derivatives
with
glycine
via
a
1,5-hydrogen
transfer
(1,5-HAT)
process
has
been
realized.
The
reaction
was
characterized
by
redox-neutral
mild
conditions,
good
yields,
excellent
enantioselectivity,
broad
substrate
scope.
This
protocol
provides
straightforward
efficient
strategy
to
prepare
highly
valuable
enantioenriched
noncanonical
α-amino
acids.
Moreover,
the
potential
synthetic
value
this
demonstrated
in
late-stage
dipeptides
high
diastereomeric
ratio.
European Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 21, 2025
Abstract
A
photoredox‐catalyzed
decarboxylative
C(
sp
3
)−H
alkylation
of
glycine
derivatives,
utilizing
(+)/(−)‐camphorsultam
as
a
chiral
auxiliary
and
alkyl
N
‐hydroxyphthalimide
(NHP)
ester
radical
precursor,
has
been
developed,
providing
an
efficient
approach
for
the
stereoselective
synthesis
valuable
enantioenriched
unnatural
α
‐alkylated
amino
acid
derivatives.
The
methodology
operates
under
mild
conditions,
demonstrates
broad
substrate
tolerance,
exhibits
excellent
stereoselectivity.
Preliminary
mechanistic
investigations
indicate
that
reaction
proceeds
via
pathway.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
We
reported
the
first
example
of
visible-light-induced
radical
cascade
cyclization
2-isocyanobiaryls
via
1,5-HAT,
which
is
characterized
by
broad
substrate
scope,
excellent
functional
group
compatibility
and
no
requirement
any
metals
base.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 20, 2025
Herein,
we
report
an
unprecedented
dual
photoexcited
palladium
and
photoredox-catalyzed
remote
C(sp3)-H
acylation
of
amides
free
external
acylating
reagents
through
sequential
N-O/C-H/C-O
bond
cleavage
chemoselective
C-C
formation.
This
catalytic
system
shows
high
efficiency,
good
atom
economy
by
deletion
oxygen,
diverse
functional
group
tolerance.
Experimental
investigation
the
reaction
mechanism
revealed
that
O-acyl
hydroxamides
enabled
generated
alkyl
radicals
via
a
1,5-HAT
process
mediated
amidyl
carboxylate
complex,
which,
undergoing
phosphoranyl
radical-mediated
C-O
cleavage,
leads
to
coupling
with
deliver
final
products.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Fluorine
and
nitrogen
form
a
successful
partnership
in
organic
synthesis,
medicinal
chemistry,
material
sciences.
Although
fluorine-nitrogen
chemistry
has
long
rich
history,
this
field
received
increasing
interest
made
remarkable
progress
over
the
past
two
decades,
driven
by
recent
advancements
transition
metal
organocatalysis
photochemistry.
This
review,
emphasizing
contributions
from
2015
to
2023,
aims
update
state
of
art
synthesis
applications
nitrogen-based
organofluorine
functional
molecules
chemistry.
In
dedicated
sections,
we
first
focus
on
fluorine-containing
reagents
organized
according
type
groups
attached
nitrogen,
including
N-F,
N-RF,
N-SRF,
N-ORF.
review
also
covers
nitrogen-linked
building
blocks,
catalysts,
pharmaceuticals,
agrochemicals,
underlining
these
components'
broad
applicability
growing
importance
modern
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 19, 2025
1,2,4-Triazine-3,5(2H,4H)-diones
are
widely
present
in
various
drug
molecules
and
bioactive
molecules.
A
visible-light-driven
C-H
alkylation
of
1,2,4-triazine-3,5(2H,4H)-diones
via
1,2-hydrogen-atom
transfer
(1,2-HAT)
amide
radicals
is
first
reported,
providing
an
environmentally
friendly
sustainable
pathway
to
enrich
the
structural
functional
diversity
1,2,4-triazine-3,5(2H,4H)-diones.
This
novel
protocol
characterized
by
mild
metal-free
reaction
conditions,
operationally
simple
method,
good
group
tolerance.
To
our
delight,
other
heterocycles,
such
as
isoquinoline
coumarin,
also
undergo
reactions
construct
C(sp2)-C(sp3)
bonds
infrequent
1,2-HAT
under
current
conditions.
