The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(24), С. 16803 - 16816
Опубликована: Дек. 5, 2023
The
visible
light-induced
perfluoroalkyl
(RF)
radical
reactions
on
peracetylglycals
derived
from
hexoses
and
pentoses
(galactal,
glucal,
arabinal,
xylal
derivatives)
were
investigated.
Various
photocatalysts
iodides
(RF–I)
employed
as
sources
of
RF
radicals
with
LEDs
the
irradiation
source.
Particularly
noteworthy
was
use
an
Iridium
photocatalyst,
Ir[dF(CF3)ppy]2(dtbpy))PF6,
which
yielded
two
distinct
product
types
when
applied
to
glucal.
On
one
hand,
2-RF-substituted
glucal
formed,
a
trend
observed
even
utilizing
organic
dyes
photocatalysts.
other
unexpected
addition
product,
namely
1-RF-2-iodo-α-manno-configured
C-glycosyl
derivative,
also
obtained,
result
highly
regioselective
reaction
moiety
into
anomeric
carbon,
followed
by
attachment
iodine
atom
C-2
in
axial
disposition.
This
contrasted
carried
out
2-unsubstituted
glycals,
where
incipient
adds
C-2,
generating
stabilized
1-glycosyl
radical.
photocatalyzed
perfluoroalkylations
peracetyl
glycals
galactose,
arabinose,
xylose
all
afforded
good
yields
expected
vinylic
substitution
reaction.
Mechanistic
studies
revealed
that
derivatives
arise
chain
reaction,
whereas
proceed
inefficient
processes.
Chemical Communications,
Год журнала:
2022,
Номер
58(75), С. 10442 - 10468
Опубликована: Янв. 1, 2022
Fluorine
compounds
are
known
for
their
abundance
in
more
than
20%
of
pharmaceutical
and
agrochemical
products
mainly
due
to
the
enhanced
lipophilicity,
metabolic
stability
pharmacokinetic
properties
organofluorides.
Consequently,
last
decade
has
seen
enormous
growth
incorporation
a
trifluoromethyl
group
into
organic
motifs.
With
significance,
this
review
aims
provide
complete
picture
transition
metal-mediated
construction
C(sp3,
sp2,
sp)-CF3
bonds
via
C-H/X
bond
functionalization
or
addition
processes
both
aliphatic
aromatic
hydrocarbons.
Diversified
reagents
ranging
from
radical
electrophilic
nucleophilic
trifluoromethylating
agents
respective
mechanisms
have
been
further
deliberated
comprehensive
overview.
The
coverage
on
topic
is
expected
make
unique
beneficial
future
applications
enriching
community
towards
improvements
field
trifluoromethylation
reactions,
turn
improving
propensity
development
drugs.
Chemical Reviews,
Год журнала:
2022,
Номер
122(20), С. 15503 - 15602
Опубликована: Май 25, 2022
Fluorinated
carbohydrates
have
found
many
applications
in
the
glycosciences.
Typically,
these
contain
fluorination
at
a
single
position.
There
are
not
involving
polyfluorinated
carbohydrates,
here
defined
as
monosaccharides
which
more
than
one
carbon
has
least
fluorine
substituent
directly
attached
to
it,
with
notable
exception
of
their
use
mechanism-based
inhibitors.
The
increasing
attention
carbohydrate
physical
properties,
especially
around
lipophilicity,
resulted
surge
interest
for
this
class
compounds.
This
review
covers
considerable
body
work
toward
synthesis
hexoses,
pentoses,
ketosugars,
and
aminosugars
including
sialic
acids
nucleosides.
An
overview
current
state
art
glycosidation
is
also
provided.
Green Chemistry,
Год журнала:
2022,
Номер
24(24), С. 9373 - 9401
Опубликована: Янв. 1, 2022
This
review
covers
the
recent
progress
in
electrochemically
enabled
radical-mediated
aryl/alkenyl
C(sp
2
)–C(sp
3
)
cross-coupling
reactions,
including
synthetic
strategies,
plausible
mechanisms
and
further
research
outlook.
Molecules,
Год журнала:
2023,
Номер
28(18), С. 6641 - 6641
Опубликована: Сен. 15, 2023
Glycomimetics,
which
are
synthetic
molecules
designed
to
mimic
the
structures
and
functions
of
natural
carbohydrates,
have
been
developed
overcome
limitations
associated
with
carbohydrates.
The
fluorination
carbohydrates
has
emerged
as
a
promising
solution
dramatically
enhance
metabolic
stability,
bioavailability,
protein-binding
affinity
In
this
review,
methods
used
prepare
fluorinated
effects
on
physical,
chemical,
biological
characteristics
sugars,
activities
sugars
presented.
Abstract
The
functionalization
of
unsaturated
carbohydrates
is
a
powerful
approach
for
the
synthesis
variety
glycoside
derivatives,
sugar
mimics,
and
enantiomerically
pure
molecules.
This
Review
will
discuss
recently
developed
catalytic
radical
methods
glycals,
exo
‐glycals,
‐enes,
highlighting
opportunities
they
offer
new
reaction
design.
While
providing
routes
complex
carbohydrates,
transformations
sugars
overcome
limitations
that
typically
affect
classical
protocols,
such
as
use
stoichiometric
oxidants/reductants
hazardous
toxic
reagents.
Currently
unaddressed
challenges
also
be
discussed,
suggesting
directions
future
work
fostering
methodological
developments
applications
in
field.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(5), С. 1283 - 1288
Опубликована: Янв. 1, 2023
An
environmentally
friendly
electrochemical
fluorotrifluoromethylation
of
styrenes
is
developed
using
CF
3
SO
2
Na
and
Et
N·3HF
as
the
F-containing
donor
reagents.
This
synthetic
strategy
features
step
economy
sustainability.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(20), С. 4225 - 4236
Опубликована: Янв. 1, 2023
An
efficient
trifluoromethylation
of
2-isocyanobiaryls
was
developed
through
the
constant
current
electrolysis,
employing
sodium
trifluoromethanesulfinate
(CF3SO2Na)
as
trifluoromethyl
source.
The
method
enabled
syntheses
a
series
6-(trifluoromethyl)phenanthridine
derivatives
in
moderate
to
high
yields
under
metal-
and
oxidant-free
conditions.
A
gram-scale
synthesis
highlights
synthetic
versatility
reported
protocol.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 13, 2025
Fluorination
has
demonstrated
the
potential
to
improve
physicochemical
and
enzymatic
properties
of
carbohydrates.
Hydrotrifluoromethylation
is
an
emerging
reaction
introduce
trifluoromethyl
groups.
However,
hydrotrifluoromethylation
glycals
been
challenging
because
lack
regioselectivity
stereoselectivity.
Herein,
we
describe
efficient,
highly
selective,
broadly
applicable
photoinduced
strategy
using
cost-effective
sodium
trifluoromethanesulfonate
give
1,2-dideoxy-2-trifluoromethyl
sugars.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(17), С. 4708 - 4715
Опубликована: Янв. 1, 2024
A
simple
and
practical
visible
light-driven
photoredox-catalyzed
three-component
carbotrifluoromethylation
of
alkenes
is
revealed
for
the
synthesis
1,4-bis(trifluoromethylated)
compounds.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(8)
Опубликована: Июнь 27, 2023
Abstract
A
green
electrochemical
C(sp
2
)−H
trifluoromethylation
of
imidazo[1,2‐
a
]pyridines
by
engaging
Langlois’
reagent
is
reported.
This
oxidative
regioselective
CF
3
‐functionalization
strategy
operates
under
open
atmosphere,
in
an
undivided
cell
and
at
ambient
temperature.
Regioselective
C−CF
bond
formation
was
achieved
exclusively
applying
this
mild
protocol
exhibiting
broad
functional
group
compatibility
affording
the
desired
product
up
to
79%
isolated
yield.
Mechanistic
studies
indicated
radical
pathway
for
redox
transformation.
