Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(9)
Опубликована: Дек. 21, 2022
β-Arylethylamines
are
prevalent
structural
motifs
in
molecules
exhibiting
biological
activity.
Here
we
report
a
sequential
one-pot
protocol
for
the
1,2-aminoarylation
of
alkenes
with
hydroxylammonium
triflate
salts
and
(hetero)arenes.
Unlike
existing
methods,
this
reaction
provides
direct
entry
to
unprotected
β-arylethylamines
remarkable
functional
group
tolerance,
allowing
key
drug-oriented
groups
be
installed
two-step
process.
The
use
hexafluoroisopropanol
as
solvent
combination
an
iron(II)
catalyst
proved
essential
reaching
high-value
nitrogen-containing
molecules.
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.
Chemical Science,
Год журнала:
2021,
Номер
12(11), С. 3857 - 3870
Опубликована: Янв. 1, 2021
Among
numerous
solvents
available
for
chemical
transformations,
1,1,1,3,3,3-hexafluoro-2-propanol
(popularly
known
as
HFIP)
has
attracted
enough
attention
of
the
scientific
community
in
recent
years.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(3), С. 1187 - 1197
Опубликована: Янв. 11, 2022
The
"magic
methyl"
effect,
a
dramatic
boost
in
the
potency
of
biologically
active
compounds
from
incorporation
single
methyl
group,
provides
simple
yet
powerful
strategy
employed
by
medicinal
chemists
drug
discovery
process.
Despite
significant
advances,
methodologies
that
enable
selective
C(sp3)–H
methylation
structurally
complex
agents
remain
very
limited.
In
this
work,
we
disclose
modular,
efficient,
and
for
α-methylation
protected
amines
(i.e.,
amides,
carbamates,
sulfonamides)
means
electrochemical
oxidation.
Mechanistic
analysis
guided
our
development
an
improved
protocol
on
basis
classic
Shono
oxidation
reaction,
which
features
broad
reaction
scope,
high
functional
group
compatibility,
operational
simplicity.
Importantly,
system
is
amenable
to
late-stage
functionalization
targets
containing
basic
nitrogen
groups
are
prevalent
medicinally
agents.
When
combined
with
organozinc-mediated
C–C
bond
formation,
enabled
direct
myriad
amine
derivatives
including
those
have
previously
been
explored
effect.
This
synthesis
thus
circumvents
multistep
de
novo
currently
necessary
access
such
has
potential
accelerate
efforts.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(29), С. 13415 - 13425
Опубликована: Июль 15, 2022
The
electrophilic
halogenation
of
arenes
is
perhaps
the
simplest
method
to
prepare
aryl
halides,
which
are
important
structural
motifs
in
agrochemicals,
materials,
and
pharmaceuticals.
However,
nucleophilicity
weakened
by
electron-withdrawing
substituents,
whose
reactions
usually
require
harsh
conditions
lead
limited
substrate
scopes
applications.
Therefore,
containing
groups
(EWGs)
complex
bioactive
compounds
under
mild
has
been
a
long-standing
challenge.
Herein,
we
describe
Brønsted
acid-catalyzed
with
substituents
conditions,
providing
an
efficient
protocol
for
halides.
hydrogen
bonding
acid
protic
solvent
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
enables
this
transformation
thus
solves
problem.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(5), С. 2355 - 2363
Опубликована: Окт. 22, 2020
Abstract
The
regio‐
and
enantioselective
(3+3)
cycloaddition
of
nitrones
with
2‐indolylmethanols
was
accomplished
by
the
cooperative
catalysis
hexafluoroisopropanol
(HFIP)
chiral
phosphoric
acid
(CPA).
Using
this
approach,
a
series
indole‐fused
six‐membered
heterocycles
were
synthesized
in
high
yields
(up
to
98
%),
excellent
enantioselectivities
96
%
ee
)
exclusive
regiospecificity.
This
approach
enabled
not
only
first
organocatalytic
asymmetric
but
also
C3‐nucleophilic
2‐indolylmethanols.
More
importantly,
theoretical
calculations
elucidated
role
cocatalyst
HFIP
helping
CPA
control
reactivity
enantioselectivity
reaction,
demonstrating
new
mode
catalysis.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(6), С. 1364 - 1383
Опубликована: Янв. 1, 2021
This
review
summarizes
the
recent
progresses
(2016–2020)
in
hydride
transfer-enabled
C(sp3)–H
activation
according
to
reaction
types,
categorized
into
intramolecular/intermolecular
functionalization,
and
reduction.
Chinese Journal of Chemistry,
Год журнала:
2020,
Номер
38(6), С. 583 - 589
Опубликована: Фев. 27, 2020
Summary
of
main
observation
and
conclusion
An
atroposelective
synthesis
a
new
class
3,3’‐bisindoles
bearing
axial
central
chirality
has
been
established
via
catalytic
asymmetric
addition
reactions
using
isatin‐derived
imines
as
electrophiles
(23
examples,
up
to
80%
yield,
>
95
:
5
dr,
98
2
er).
This
approach
takes
advantage
chiral
phosphoric
acid‐catalyzed
dynamic
kinetic
resolution
2‐substituted
nucleophilic
such
substrates
with
imines.
In
this
approach,
acted
competent
due
their
high
reactivity
bulky
size,
which
provided
an
easy
access
axially
3,3'‐bisindoles
incorporated
biologically
important
3‐aminooxindole
unit.
greatly
expanded
the
generality
applicability
strategy
for
enantioenriched
3,3’‐bisindole
derivatives
both
chirality.
Journal of The Electrochemical Society,
Год журнала:
2020,
Номер
167(15), С. 155509 - 155509
Опубликована: Янв. 12, 2020
Because
of
the
necessity
carry
out
electrolysis
reactions
with
considerable
quantity
organic
molecules,
balance
between
solubility
starting
material,
solution
conductivity
and
electrochemical
stability
medium
intermediates
are
key
factors
in
electrosynthesis.
HFIP
has
several
properties
that
favor
its
use
this
research
area
as
solvent,
among
them,
high
hydrogen-bond
donor
opened
possibility
fine
tuning
reactivity,
mainly
anodic
because
helpful
effect
on
positive
intermediates.
The
cost
solvent
limited
broad
application
chemistry,
including
electrosynthesis,
but
using
mixtures
other
cosolvents
demonstrated
to
help
expand
without
losing
beneficial
In
recent
years
(HFIP/MeOH,
HFIP/CH
2
Cl
,
HFIP/H
O,
HFIP/ACN,
HFIP/MeNO
)
have
permitted
control
chemical
microstructure
media
let
adjust
fulfill
review
will
be
discussed
general
reported
synthetic
transformations
well
where
been
electrogenerated
This
approach
succeeded
Chemical Communications,
Год журнала:
2022,
Номер
58(61), С. 8516 - 8519
Опубликована: Янв. 1, 2022
Gold
catalysis
has
witnessed
immense
evolution
in
recent
years,
yet
it
still
requires
the
use
of
activators
to
render
common
[AuCl(L)]
complexes
catalytically
active.
Herein,
H-bonding
donor
properties
hexafluoroisopropanol
(HFIP)
are
utilized
for
Au-Cl
bond
activation
and
ancillary
ligand
counteranion
effects
on
cycloisomerization
reactions
showcased
HFIP
as
solvent.
