Angewandte Chemie,
Год журнала:
2023,
Номер
135(38)
Опубликована: Авг. 3, 2023
Abstract
Aliphatic
trifluoromethyl
ketones
are
a
type
of
unique
fluorine‐containing
subunit
which
play
significant
role
in
altering
the
physical
and
biological
properties
molecules.
Catalytic
methods
to
provide
direct
access
aliphatic
highly
desirable
yet
remain
underdeveloped,
partially
owing
high
reactivity
instability
trifluoroacetyl
radical.
Herein,
we
report
photocatalytic
synthesis
from
alkyl
bromides
with
trifluoroacetic
anhydride.
The
reaction
features
dual
visible‐light
halogen‐atom‐transfer
catalysis,
followed
by
an
enabling
radical‐radical
cross‐coupling
radical
stabilized
provides
straightforward
readily
available
cost‐effective
halides
anhydride
(TFAA).
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(38)
Опубликована: Авг. 3, 2023
Aliphatic
trifluoromethyl
ketones
are
a
type
of
unique
fluorine-containing
subunit
which
play
significant
role
in
altering
the
physical
and
biological
properties
molecules.
Catalytic
methods
to
provide
direct
access
aliphatic
highly
desirable
yet
remain
underdeveloped,
partially
owing
high
reactivity
instability
trifluoroacetyl
radical.
Herein,
we
report
photocatalytic
synthesis
from
alkyl
bromides
with
trifluoroacetic
anhydride.
The
reaction
features
dual
visible-light
halogen-atom-transfer
catalysis,
followed
by
an
enabling
radical-radical
cross-coupling
radical
stabilized
provides
straightforward
readily
available
cost-effective
halides
anhydride
(TFAA).
Organic Letters,
Год журнала:
2023,
Номер
26(1), С. 100 - 105
Опубликована: Дек. 26, 2023
Herein,
we
report
a
photoredox
enabled
defluorinative
benzylation
of
trifluoromethyl
alkenes
with
readily
available
alkylarenes,
which
provides
convenient
access
to
series
structurally
valuable
benzylated
gem-difluoroalkenes
under
mild
reaction
conditions.
The
synthetic
value
this
protocol
has
been
demonstrated
by
the
transformations
several
substrates
bearing
drug
moieties,
gram-scale
reactions,
and
various
further
derivatizations
gem-difluoroalkene
products.
preliminary
mechanistic
investigations
suggest
pathway
rate-determining
benzyl
C–H
bond
cleavage
toluene
followed
benzylic
radical
formation.
RSC Sustainability,
Год журнала:
2024,
Номер
2(8), С. 2169 - 2189
Опубликована: Янв. 1, 2024
This
review
describes
the
recent
advancements
in
visible
light-induced
bromine
radical
enhanced
hydrogen
atom
transfer
(HAT)
reactions
organic
synthesis.
Organic Letters,
Год журнала:
2023,
Номер
25(41), С. 7529 - 7534
Опубликована: Окт. 11, 2023
The
electrochemical
synthesis
of
N-aroylsulfoximines
features
the
use
tetra-n-butylammonium
iodide
(TBAI)
as
medium
and
a
broad
substrate
scope,
thus
affording
wide
range
N-aroylated
sulfoximines
in
moderate
to
good
yields.
advantages
this
strategy
are
augmented
by
mild
reaction
conditions
that
external
oxidant-free,
ligand-free,
easy
scale
up
gram
scale.
Both
control
experiments
mechanistic
studies
revealed
whole
process
proceeded
through
palladium
(II/IV/II)
catalytic
cycle.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9186 - 9190
Опубликована: Дек. 15, 2023
The
photoredox/PPh3-mediated
cyclization
of
2-isocyanobiaryls
has
been
developed.
A
substantial
range
functional-group-rich
phenanthridine
derivatives
were
synthesized
at
room
temperature
in
a
highly
selective
and
atom-economic
manner.
Mechanistic
studies
suggested
that
the
process
is
probably
mediated
both
by
Ph3P
radical
cation
with
key
1,2-hydride
transfer
hydrogen
atom
generated
through
O–H
bond
homolytic
cleavage
Ph3P–OH
intermediate.
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5285 - 5289
Опубликована: Июнь 13, 2024
The
C-H
alkylation
of
benzyl
alcohols
with
α-ketoacid
derivatives
was
achieved
in
the
presence
thiobenzoic
acid
or
without
Ru
Ir
photoredox
catalysts.
serves
as
a
photoexcited
single-electron
reducing
reagent
and
hydrogen
atom
transfer
catalyst,
while
addition
metal
catalyst
assists
electron
improves
reaction
efficiency.
Various
functional
groups
were
tolerant
conditions,
sterically
hindered
diols
produced
good
to
high
yield.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12591 - 12609
Опубликована: Авг. 14, 2024
The
incorporation
of
gem-difluoromethylene
units
into
organic
molecules
remains
a
formidable
challenge.
Conventional
methodologies
for
constructing
aryldifluoromethyl
derivatives
relied
on
the
use
high-functional
fluorinating
regents
under
harsh
conditions.
Herein,
we
report
general
and
efficient
photoredox
catalytic
systems
defluoroalkylation
readily
available
trifluoromethylarenes
through
selective
C–F
cleavage
to
deliver
gem-difluoromethyl
radicals
which
proceed
reductive
addition
both
electron-donating
withdrawing
alkenes
transition-metal
free
Mechanistic
studies
reveal
that
thiol
serves
as
photocatalyst
HAT
reagent
visible
light
irradiation.
This
synergistic
photocatalysis
catalysis
protocol
exhibits
ample
salient
features
such
high
chemo-
regioselectivity,
broad
substrate
scope,
amenable
gram-scale
synthesis
late-stage
modification
bioactive
molecules.
Molecules,
Год журнала:
2024,
Номер
29(24), С. 5848 - 5848
Опубликована: Дек. 11, 2024
Oxazoles
are
important
five-membered
heterocycles
that
contain
both
nitrogen
and
oxygen
atoms.
Due
to
their
wide
range
of
biological
activities,
many
oxazoles
demonstrate
potential
for
extensive
application
in
various
fields,
including
medicinal
chemistry.
Trifluoromethyl
carbinol,
an
pharmacophore,
contains
trifluoromethyl
hydroxyl
groups
is
common
molecules
with
activities.
Constructing
a
carbinol
unit
undoubtedly
valuable
expanding
the
chemical
space
drug
discovery.
In
this
study,
simple
efficient
method
was
developed
synthesis
containing
CF3-substituted
alcohol
via
tandem
cycloisomerization/hydroxyalkylation
N-propargylamides
trifluoropyruvates
through
rational
Lewis
acid
catalytic
mechanism.
This
Zn(OTf)2-catalyzed
synthetic
protocol
operationally
provides
series
moderate
good
yields.
The
demonstrates
broad
substrate
scope,
high
functional
group
tolerance,
atom
economy
can
achieve
gram-level
reactions,
indicating
strong
possibility
its
practical
application.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(23), С. 3275 - 3280
Опубликована: Июль 27, 2023
Comprehensive
Summary
α‐Fluoroalkyl
(R
f
)
alcohols
are
privileged
motifs
in
drugs
and
pharmaceutically
active
compounds.
As
such,
it
is
highly
desirable
to
develop
efficient
methods
for
assembling
these
scaffolds.
Herein,
a
visible‐light‐induced
cascade
radical
cyclization
of
alkenyl
fluoroalkyl
ketones
developed,
producing
variety
decorate
α‐R
cycloalkanols
promising
yields
with
up
>20
:
1
dr
selectivity.
A
chain
mechanism
involving
an
intramolecular
addition
the
carbonyl
group
subsequent
intermolecular
hydrogen
atom
transfer
(HAT)
has
been
proposed.
Density
functional
theory
(DFT)
calculations
indicate
that
fluorine
effect
contributes
carbonyls
by
lowering
π*
(C=O)
orbital
energy
COR
barrier
HAT
between
alkoxy
radicals
THF,
which
may
be
valuable
controllable
transformations
fluorinated
molecules.
