Abstract
N-(Difluoropropenyl)amides/amines
are
an
important
class
of
fluorinated
compounds.
Here,
we
report
efficient
method
for
synthesizing
these
compounds
without
the
use
transition
metals.
Under
simple
base-promoted
conditions,
3-bromo-3,3-difluoroprop-1-ene
reacts
with
N-methylanilines
or
N-arylacrylamides,
elimination
one
molecule
HBr,
to
give
target
compound.
Another
difluoroalkenes
is
reaction
2-bromo-3,3,3-trifluoroprop-1-ene
indole
its
analogues.
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.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(43)
Опубликована: Сен. 13, 2023
Abstract
The
utilization
of
aryl
radicals
as
open‐shelled
intermediates
has
become
an
essential
tool
for
both
conventional
and
state‐of‐the‐art
synthetic
chemistry.
However,
the
current
methods
generating
are
still
inefficient,
greatly
impeding
their
practical
applications.
Encouragingly,
sulfonium
salts
have
emerged
appealing
sources
a
wide
range
transformations
aimed
at
creating
novel
chemical
bonds
driven
by
distinctive
structural
attributes
tendencies.
This
review
primarily
focuses
on
specific
reaction
mechanisms
underlying
cleavage
C−S
in
salts,
leading
to
generation
corresponding
within
diverse
conditions.
Green Chemistry,
Год журнала:
2023,
Номер
25(17), С. 6733 - 6738
Опубликована: Янв. 1, 2023
A
metal
free,
visible-light
driven
α-C(sp
3
)−H
gem-difluoroallylation
of
glycine
derivatives
with
CF
-alkenes
and
1,3-enynes
is
presented
under
redox-neutral
conditions
good
yields
excellent
functional
group
compatibility.
Organic Letters,
Год журнала:
2023,
Номер
25(13), С. 2294 - 2299
Опубликована: Март 23, 2023
A
concise
and
efficient
hydrodefluorination
process
was
developed
for
the
synthesis
of
gem-difluoroalkenes.
This
reaction
employs
rongalite
as
a
masked
proton
source
does
not
require
any
additional
catalysts
or
reductants.
Notably,
trifluoromethyl
alkenes
having
both
terminal
internal
double
bonds
are
compatible
with
this
process,
allowing
wider
range
substrates.
The
successful
late-stage
functionalizations
pharmaceuticals
gram-scale
syntheses
were
used
to
demonstrate
viability
method.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(19)
Опубликована: Март 18, 2024
Abstract
Unnatural
amino
acids,
and
their
synthesis
by
the
late‐stage
functionalization
(LSF)
of
peptides,
play
a
crucial
role
in
areas
such
as
drug
design
discovery.
Historically,
LSF
biomolecules
has
predominantly
utilized
traditional
synthetic
methodologies
that
exploit
nucleophilic
residues,
cysteine,
lysine
or
tyrosine.
Herein,
we
present
photocatalytic
hydroarylation
process
targeting
electrophilic
residue
dehydroalanine
(Dha).
This
possesses
an
α
,
β
‐unsaturated
moiety
can
be
combined
with
various
arylthianthrenium
salts,
both
batch
flow
reactors.
Notably,
setup
proved
instrumental
for
efficient
scale‐up,
paving
way
unnatural
acids
peptides
substantial
quantities.
Our
approach,
being
inherently
mild,
permits
diversification
even
when
they
contain
sensitive
functional
groups.
The
readily
available
salts
facilitate
seamless
integration
Dha‐containing
wide
range
arenes,
blueprints,
natural
products,
culminating
creation
unconventional
phenylalanine
derivatives.
synergistic
effect
high
group
tolerance
modular
characteristic
aryl
electrophile
enables
peptide
conjugation
ligation
conditions.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9124 - 9129
Опубликована: Ноя. 17, 2023
Herein,
we
describe
a
novel
and
efficient
photoredox
catalytic
Cα
radical
addition/defluoroalkylation
coupling
reaction
between
α-trifluoromethyl
alkenes
N-trifluoroethyl
hydroxylamine.
A
series
of
gem-difluoroallylated
α-trifluoromethylamines
were
synthesized
by
the
addition
enabled
1,2-H
shift
in
situ-generated
radical.
Notably,
this
protocol
is
distinguished
its
mild
conditions,
easy
operation,
excellent
functional
group
tolerability.
Green Chemistry,
Год журнала:
2024,
Номер
26(17), С. 9371 - 9377
Опубликована: Янв. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 8, 2024
Aryl
thianthrenium
salts
are
valuable
in
photocatalysis
but
traditionally
require
external
electron
donors
for
activation.
This
study
introduces
an
energy
transfer
(EnT)
strategy
the
activation
of
aryl
using
2,3,4,5,6-penta(carbazol-9-yl)benzonitrile
(5CzBN)
as
a
metal-free
photocatalyst,
eliminating
need
donors.
Utilizing
this
EnT
approach,
we
achieve
C-H
deuteration
arenes
under
visible
light
with
CDCl
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5232 - 5277
Опубликована: Янв. 1, 2024
This
review
describes
recent
advances
in
the
generation
of
aryl
radicals
using
light
and
electricity.
Such
modern
techniques
allow
for
efficient
energy
resource
utilization,
thus
providing
more
sustainable
radical
arylation
methods.
