Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(34)
Опубликована: Июнь 3, 2024
This
review
article
describes
the
development
of
use
aluminum
compounds
in
chemistry
frustrated
Lewis
pairs
(FLPs)
over
last
14
years.
It
also
discusses
synthesis,
reactivity
and
catalytic
applications
intermolecular,
intramolecular
so-called
hidden
FLPs
with
phosphorus,
nitrogen
carbon
bases.
The
intrinsically
higher
acidity
compared
to
their
boron
analogs
opens
up
different
reaction
pathways.
results
are
presented
a
more
or
less
chronological
order.
is
shown
that
Al
react
variety
polar
non-polar
substrates
form
both
stable
adducts
reversibly
activate
bonds.
Consequently,
some
title
were
such
as
dimerization
alkynes,
hydrogenation
tert-butyl
ethylene
imines,
C-F
bond
activation,
reduction
CO
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(17)
Опубликована: Апрель 3, 2024
Abstract
β
‐fluorocarbanions
have
garnered
considerable
attention
for
their
dual
reactivity
in
nucleophilic
processes
and
‐fluorine
elimination.
In
this
study,
a
thorough
computational
analysis
was
conducted
to
explore
the
reactions
of
α
‐(trifluoromethyl)styrenes
with
2‐pyridones
delineate
factors
determining
protonation
or
defluorination
pathways
situ
generated
under
varied
basic
conditions.
Our
findings
illuminate
critical
role
organobase
basicity
steering
direction
competitive
elimination
reactions.
We
propose
use
p
K
aH
values
organobases
as
quantitative
indicator
discerning
predominant
reaction
pathways.
This
provides
an
efficient
approach
predict
control
outcome,
facilitating
deliberate
design
leverage
unique
realm
fluorine
chemistry.
Through
the
prosperity
of
organofluorine
chemistry
in
modern
organic
synthesis,
perfluorinated
compounds
are
now
abundant
and
widely
available.
Consequently,
these
substances
become
attractive
starting
materials
for
production
complex,
multifunctional
fluorinated
molecules.
However,
inherent
challenges
associated
with
activation
discrimination
C–F
bonds
typically
lead
to
overdefluorination
as
well
functional
group
incompatibility.
To
address
problems,
our
utilized
a
rationally
designed
organophosphorus
reagent
that
promoted
mild
selective
manipulation
single
bond
trifluoromethyl
pentafluoroethyl
ketones
via
an
interrupted
Perkow-type
reaction,
which
allowed
replacement
fluorine
more
labile
synthetically
versatile
congeners
such
chlorine,
bromine,
iodine.
The
resulting
α-haloperfluoroketones
have
two
reactive
units
orthogonal
properties
would
be
suitable
subsequent
structural
diversification.
DFT
calculations
identified
favorable
P–F
interaction
crucial
factor
from
both
thermodynamic
kinetic
viewpoints.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 6, 2025
The
unique
properties
of
fluorinated
organic
compounds
have
received
intense
interest
and
conquered
a
myriad
applications
in
the
chemical
pharmaceutical
sciences.
Today,
an
impressive
range
alkyl
fluorides
are
commercially
available,
there
many
practical
methods
to
make
them
exist.
However,
unmatched
stability
inertness
C–F
bond
largely
limited
its
synthetic
value,
which
is
very
different
from
widely
accepted
utility
chlorides,
bromides,
iodides
that
serve
everyday
as
"workhorse"
building
blocks
countless
carbon–carbon
forming
reactions.
This
study
demonstrates
high-yielding
functionalization
under
mild
conditions,
i.e.,
at
temperatures
low
−78
°C,
short
reaction
times
with
unconventional
chemoselectivity.
Cryogenic
Csp3–F
cleavage
using
fluorophilic
organoaluminum
together
fast
nucleophile
transfer
intermediate
ate
complexes
forge
bonds
unactivated
primary,
secondary,
tertiary
alike.
method,
exploits
Al–F
thermodynamic
driving
force,
highly
selective
toward
functionalization,
whereas
other
functional
groups
including
chloride,
bromide,
iodide,
aryl
halide,
alkenyl,
alkynyl,
difluoroalkyl,
trifluoromethyl,
ether,
ester,
hydroxyl,
acetal,
heteroaryl,
nitrile,
nitro,
amide
tolerated,
unexpected
reversal
long-standing
main
group
organometallic
halide
cross-coupling
reactivity
compatibility
patterns.
As
result,
strongest
single
chemistry
can
now
be
selectively
targeted
arylation,
alkylation,
alkenylation,
alkynylation
reactions
used
late-stage
complementary
currently
available
methods.
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
A
practical
strategy
for
the
preparation
of
a
series
iron(II)
complexes
has
been
developed.
This
methodology
features
in
situ
esterification
CF3
group
on
backbone
PIP–CF3
ligand
(HPIP
=
3-(pyridin-2-yl)imidazo[1,5-a]pyridine,
3-(pyridin-2-yl)-1-(trifluoromethyl)imidazo[1,5-a]pyridine)
by
wide
range
alcohols.
Treatment
FeCl2·4H2O
with
EtOH
under
solvothermal
conditions
leads
to
formation
[Fe(PIP–COOEt)2Cl2]
(1),
[Fe2(PIP–COOEt)2Cl4]
(2),
and
[Fe(PIP–COOEt)Cl2]
(2′)
(PIP–COOEt
ethyl
3-(pyridin-2-yl)imidazo[1,5-a]pyridine-1-carboxylate).
serves
as
solvent
is
also
involved
group.
The
protocol
broad
substrate
scope.
moiety
could
be
esterified
alcohol
substrates.
Compounds
[Fe(PIP–COOnPr)2Cl2]
(3),
[Fe2(PIP–COOnPr)2Cl4]
(4),
[Fe2(PIP–COOiPr)2Cl4]
(5),
[Fe(PIP–CF3)2Cl2]·iPrOH
(6·iPrOH)
were
isolated,
their
structures
characterized.
mechanism
was
proposed
examining
transformations.
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.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(16), С. 4479 - 4486
Опубликована: Янв. 1, 2024
A
highly
selective
photocatalytic
deuterodefluorination
of
α,
α
-difluoroarylacetic
esters
and
amides
with
D
2
O
is
presented.
The
use
a
catalytic
amount
disulfide
crucial
for
both
the
C–F
bond
activation
C–D
formation.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(33)
Опубликована: Апрель 11, 2024
Photoinduced
single-electron
reduction
is
an
efficient
method
for
the
mono-selective
activation
of
C-F
bond
on
a
trifluoromethyl
group
to
construct
difluoroalkyl
group.
We
have
developed
electron-donor-acceptor
(EDA)
complex
mediated
transfer
(EDA-SET)
α,α,α-trifluoromethyl
arenes
in
presence
lithium
salt
give
α,α-difluoroalkylarenes.
The
was
realized
by
iodide
and
triethylamine,
two
common
feedstock
reagents.
Mechanistic
studies
revealed
generation
α,α-difluoromethyl
radical
defluorination,
followed
addition
alkenes.
Lithium
interacted
with
fluorine
atom
promote
photoinduced
EDA
complex.
Computational
indicated
that
lithium-assisted
defluorination
occurred
concertedly.
call
this
phenomenon
fluoride-coupled
electron
(FCET).
FCET
novel
approach
synthesis
organofluorine
compounds.
Dalton Transactions,
Год журнала:
2024,
Номер
53(35), С. 14582 - 14586
Опубликована: Янв. 1, 2024
Kinetic
frustrated
Lewis
pairs
(FLP)
allow
facile
cleavage
of
a
number
E-H
bonds
(E
=
H,
Si,
C,
B)
where
both
the
base
and
acid
are
involved
in
bond
activation
transition
state.
More
recently,
kinetic
FLP
systems
have
been
extended
to
C-X
(X
F,
Cl,
Br)
bonds.
We
report
on
role
sodium
tetrakis(pentafluorophenyl)borate
benzylation
triarylphosphines,
cation
phosphine
support
type
