Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(47)
Опубликована: Сен. 16, 2022
Controlling
regioselectivity
in
C-H
functionalizations
is
a
key
challenge
chemical
method
development.
In
arenes,
are
most
difficult
to
direct
towards
the
group
furthest
away
from
substituent,
its
para
position.
We
herein
demonstrate
how
para-C-H
arylation
of
anilines
with
non-activated
aryl
halides,
elusive
date,
achieved
by
base-assisted
"metalla-tautomerism"
approach.
A
proton
abstracted
aniline
substrate
and
replaced
an
arylpalladium
species,
generated
halide
coupling
partner.
this
step,
palladium
directed
N-
tautomeric
position
large
phosphine
ligand
combined
triphenylmethyl
shielding
group.
The
easily
installed
removed,
can
be
recycled.
Chemical Reviews,
Год журнала:
2022,
Номер
122(15), С. 12544 - 12747
Опубликована: Июль 17, 2022
1,1,1,3,3,3-Hexafluoroisopropanol
(HFIP)
is
a
polar,
strongly
hydrogen
bond-donating
solvent
that
has
found
numerous
uses
in
organic
synthesis
due
to
its
ability
stabilize
ionic
species,
transfer
protons,
and
engage
range
of
other
intermolecular
interactions.
The
use
this
exponentially
increased
the
past
decade
become
choice
some
areas,
such
as
C–H
functionalization
chemistry.
In
review,
following
brief
history
HFIP
an
overview
physical
properties,
literature
examples
reactions
using
or
additive
are
presented,
emphasizing
effect
each
reaction.
Chemical Communications,
Год журнала:
2020,
Номер
56(78), С. 11548 - 11564
Опубликована: Янв. 1, 2020
Hexafluoroisopropanol
(HFIP)
is
a
solvent
with
unique
properties
that
has
recently
gained
attention
for
promoting
wide
range
of
challenging
chemical
reactions.
It
was
initially
believed
HFIP
almost
exclusively
involved
in
the
stabilization
cationic
intermediates,
owing
to
its
high
polarity
and
low
nucleophilicity.
However,
many
cases,
mechanism
action
appears
be
more
complex.
Recent
findings
reveal
Lewis
Brønsted
acid-catalyzed
transformations
conducted
additionally
involve
cooperation
between
catalyst
hydrogen-bond
clusters,
akin
Lewis-
or
acid-assisted-Brønsted
acid
catalysis.
This
feature
article
showcases
remarkable
versatility
reactions,
an
emphasis
on
examples
yielding
mechanistic
insight.
ACS Catalysis,
Год журнала:
2020,
Номер
10(18), С. 10794 - 10802
Опубликована: Авг. 26, 2020
Aniline
derivatives
are
frequently
encountered
in
molecules
of
industrial
relevance
such
as
dyes
or
antioxidants,
which
make
the
development
synthetic
methods
for
functionalization
these
privileged
structures
highly
sought-after.
A
general
protocol
hydroarylation
electronically
diverse
alkenes
with
anilines
would
be
ideal
to
provide
densely
functionalized
compounds.
However,
this
transformation
has
been
underexplored
compared
more
traditional
unactivated
because
significant
challenges
associated
control
selectivity
and
its
substrate
tolerance.
Herein,
we
describe
a
selective,
versatile,
user-friendly
ortho-C-alkylation
that
hinges
on
beneficial
combination
Lewis
acid
(Ca(II))
hexafluoroisopropanol
solvent.
This
allows
extension
deactivated
styrenes
demonstrates
remarkable
improved
reactivity
regarding
aliphatic
alkenes,
styrene
derivatives,
dienes.
In
addition,
DFT
computations
were
performed
which,
combined
experimental
observations,
suggest
nearly
concerted
mechanism
impart
ortho-selectivity.
ACS Organic & Inorganic Au,
Год журнала:
2024,
Номер
4(3), С. 287 - 300
Опубликована: Март 4, 2024
In
the
past
5
years,
hexafluoroisopropanol
(HFIP)
has
been
used
as
a
unique
solvent
or
additive
to
enable
challenging
transformations
through
substrate
activation
and
stabilization
of
reactive
intermediates.
this
Review,
we
aim
at
describing
difunctionalization
processes
which
were
unlocked
when
HFIP
was
involved.
Specifically,
focus
on
cyclizations
additions
alkenes,
alkynes,
epoxides,
carbonyls
that
introduce
wide
range
functional
groups
interest.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3316 - 3320
Опубликована: Апрель 10, 2024
Operationally
simple
and
generally
applicable
arene
nitration
with
cheap
easily
accessible
chemicals
has
been
a
long-sought
transformation
in
the
synthetic
organic
community.
In
this
work,
we
realized
goal
nontoxic
inexpensive
Fe(NO3)3·9H2O
as
nitro
source
recyclable
solvent
hexafluoroisopropanol
promotor
via
network
of
hydrogen-bonding
interactions.
As
result
relative
mildness
high
reliability
protocol,
late-stage
various
highly
functionalized
natural
products
commercially
available
drugs
was
realized.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
58(2), С. 281 - 298
Опубликована: Янв. 3, 2025
ConspectusControlling
selectivity
through
manipulation
of
reaction
intermediates
remains
one
the
most
enduring
challenges
in
organic
chemistry,
providing
novel
solutions
for
selective
C-C
π-bond
functionalization.
This
approach,
guided
by
activation
principles,
provides
an
effective
method
functional
group
installation,
enabling
direct
synthesis
molecules
that
are
inaccessible
conventional
pathways.
In
particular,
functionalization
N-conjugated
allenes
and
alkynes
has
emerged
as
a
promising
research
focus,
driven
advances
controlling
reactive
strategies.
this
regard,
our
group,
alongside
others,
established
some
new
approaches
have
suitable
platform
functionalized
enamides.
Account
reviews
recent
developments
field,
highlighting
modes
reactivity
selectivity,
atom-economical
functionalizations,
strategies
regio-
stereocontrol,
while
mechanistic
insights
into
related
transformations.Our
study
is
systematically
organized
two
sections
based
on
substrate
type
chronological
progression.
first
section,
we
establish
allenamide-derived
intermediates,
both
allenamide-alkyne
(AA)
cross-coupling
few
electrophile-promoted
hydrofunctionalization
reactions.
The
unprecedented
Pd-catalyzed
achieved
neighboring
chelation,
with
phosphine
ligand
selection
outcome.
parallel,
functionalizations─including
haloalkynylation,
hydrooxycarbonylation,
hydrodifluoroalkylation,
intermolecular
hydroamination─are
strategic
electrophiles
or
their
precursors.Additionally,
findings
demonstrate
how
ynamides'
toward
nucleophiles,
controlled
activator
modulation,
expands
scope
accessible
transformations.
Key
include:
(1)
chemoselective
[2
+
2
2]
annulation
efficient
trapping
N-arylated
nitrilium
ynamides,
(2)
divergent
C-H
indole-derived
vinylogous
ynamides
metal
via
intramolecular
hydroarylation,
(3)
bromoalkynylation-enabled
migration
1,3-alkynyl
shift.The
final
section
explores
N-electron
polarization
1,3-enynes
enables
chemoselectivity
metal-free
inter-
couplings
indole
substrates.
Our
modulating
conjugation
within
enyne
skeleton─through
linear
cross
conjugation─can
pathways
control
product
selectivity.This
aims
to
stimulate
broader
intermediate-controlled
activated
π-systems.
Future
directions
include
advanced
design,
strategies,
deeper
studies
enable
rational
development.
Organic Letters,
Год журнала:
2021,
Номер
23(3), С. 1081 - 1085
Опубликована: Янв. 13, 2021
The
construction
of
functional
N-containing
active
biomolecules
and
bidentate
nitrogen
ligands
by
electroreductive
pyridylation
N-heteroaromatics
is
an
eye-catching
task
challenge.
A
simple
practical
electroreductive-induced
C3
quinoxalin-2(1H)-ones
with
readily
available
cyanopyridines
reported.
More
than
36
examples
are
supplied,
the
reaction
performed
in
>95%
yield.
present
protocol
provides
a
convenient,
efficient,
gram-scale
synthesis
strategy
for
series
new
types
potential
ligands.
Hexafluoroisopropanol
(HFIP)-mediated
terminal
selective
heteroarylation
of
allenamides
has
been
accomplished
through
H-bonding
network-enabled
substrate
activation
in
a
robust
fashion.
This
strategy
features
cascade
process
involving
sequential
nucleophilic
addition
followed
by
electrophilic
heteroaromatic
substitution
and
is
well
suited
for
late-stage
functionalization
complex
bioactive
molecules.
The
elucidation
the
underlying
mechanism
was
achieved
comprehensive
combination
several
control
experiments,
kinetic
studies,
isotopic
labeling
isolation
HFIP-allenamide
intermediate
adduct.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(2), С. 946 - 953
Опубликована: Сен. 21, 2020
Pyrrolidine
and
piperidine
derivatives
bearing
halide
functional
groups
are
prevalent
building
blocks
in
drug
discovery
as
halides
can
serve
an
anchor
for
post-modifications.
In
principle,
one
of
the
simplest
ways
to
build
these
frameworks
is
haloamination
alkenes.
While
progress
has
been
made
this
field,
notably
with
development
enantioselective
versions,
reaction
still
fraught
limitations
terms
reactivity.
Besides,
a
major
question
remaining
understand
mechanism
at
work.
The
formation
haliranium
intermediate
typically
mentioned,
but
limited
mechanistic
evidence
supports
it.
Reported
here
efficient
metal-
oxidant-free
protocol
achieve
haloamidation
olefins,
promoted
by
hexafluoroisopropanol,
along
DFT
investigation
mechanism.
These
findings
should
guide
future
more
complex
transformations
field
halofunctionalization.
