European Journal of Organic Chemistry,
Год журнала:
2021,
Номер
2021(29), С. 3938 - 3969
Опубликована: Июнь 7, 2021
Abstract
Chiral
halogenated
substances
have
many
applications
in
pharmaceuticals,
agrochemicals,
and
materials,
such
as
polymers,
liquid
crystals
intermediates
synthesis.
The
presence
of
a
halogen
atom
molecule
can
large
effect
its
properties;
for
instance,
halogens
are
used
drugs
to
improve
lipophilicity,
membrane
permeability
absorption,
even
the
blood‐brain
barrier
permeability.
As
highlighted
this
review,
there
nowadays
range
highly
selective,
versatile
halogenating
reagents,
electrophilic,
nucleophilic
or
radical
nature,
which
operate
under
mild
conditions,
allowing
late‐stage
functionalization
complex
molecules
cascade
reactions.
Recent
developments
organocatalyst
design
revealed
novel
Cinchona
alkaloids
derivatives,
chiral
phosphoric
acids,
amines,
phosphines
several
bifunctional
catalysts,
mostly
thiourea‐
squaramide‐based,
introduced
chirality,
with
high
levels
enantio‐
diastereoselection,
formation
one
multiple
centers
single
synthetic
operation,
shown.
In
review
we
survey
literature
published
field
from
2014
2020.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(23), С. 3974 - 4005
Опубликована: Окт. 20, 2022
Abstract
Halogen
(fluorine,
chlorine,
bromine,
iodine)
or
chalcogen
(sulfur,
selenium)‐containing
heterocycles
are
widely
recognized
as
key
building
blocks
in
many
natural
products
and
bioactive
targets.
Catalytic
asymmetric
halogenation/chalcogenation
of
carbon‐carbon
unsaturated
bonds
via
onium
ion
transformations
efficient
methods
to
obtain
diverse
chiral
heterocyclic
backbones.
In
the
past
few
years,
catalytic
enantioselective
versions
halo/thio/seleno‐functionalizations
with
various
halogen
electrophiles
have
experienced
constant
development.
This
review
highlights
those
advances
preparing
functionalized
promoted
by
organocatalysts
metal‐based
catalysts.
magnified
image
Chemical Science,
Год журнала:
2022,
Номер
13(15), С. 4327 - 4333
Опубликована: Янв. 1, 2022
We
report
a
previously
unknown
disconnection
approach
to
valuable
fluorinated
tertiary
stereocenters
based
on
the
skeletal
modification
of
1,1-disubstituted
alkenes
by
Rh-catalyzed
carbyne
transfer.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(19)
Опубликована: Март 8, 2023
Homologation
of
trisubstituted
fluoroalkenes
followed
by
allylboration
aldehyde,
ketone
and
imine
substrates
is
suitable
for
synthesis
β-fluorohydrin
amine
products.
In
the
presence
(R)-iodo-BINOL
catalyst
enantioselectivities
up
to
99
%
can
be
achieved
formation
a
single
stereoisomer
with
adjacent
stereocenters,
which
one
tertiary
C-F
center.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(20), С. 4163 - 4180
Опубликована: Янв. 1, 2023
A
number
of
organic
transformations
have
been
achieved
using
hypervalent
iodine
reagents
under
mild
reaction
conditions.
The
use
these
as
chiral
organocatalyst
exhibited
highly
selective
asymmetric
reactions.
Abstract
The
efficient
construction
of
γ
‐chirogenic
amines
has
been
realized
via
asymmetric
hydrogenation
‐branched
N
‐phthaloyl
allylamines
by
using
a
bisphosphine‐Rh
catalyst
bearing
large
bite
angle.
desired
products
possessing
different
‐substituents
were
obtained
in
quantitative
yields
and
with
excellent
enantioselectivities
(up
to
>99%
ee).
This
protocol
provides
practical
method
for
the
preparation
amine
derivatives
such
as
famous
antidepressant
drug
Fluoxetine
50000
S/C).
mechanistic
calculations
show
an
unusual
P‐Rh‐P
trans
‐chelating
pattern
weak
interaction‐promoted
activation
mode
which
are
completely
from
traditional
cis
coordination‐promoted
metal‐catalyzed
hydrogenations.
Key
points
Novel
methodology
was
developed
synthesis
γ‐chirogenic
amines.
New
synthetic
route
well‐known
Fluoxetine.
Unusual
mechanism
information
found
bidentate
bisphosphine‐Rh‐catalyzed
hydrogenation.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
9(2), С. 499 - 516
Опубликована: Ноя. 18, 2021
Catalytic
asymmetric
halocyclization
of
olefinic
substrate
has
evolved
rapidly
and
been
well
utilized
as
a
practical
strategy
for
constructing
enantioenriched
cyclic
skeletons
in
natural
product
synthesis.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(1)
Опубликована: Ноя. 8, 2022
Abstract
A
catalysis‐based
regioselective
1,4‐fluorofunctionalization
of
trifluoromethyl
substituted
1,3‐dienes
has
been
developed
to
access
compact,
highly
functionalized
products.
The
process
allows
E
,
Z
‐mixed
dienes
be
processed
a
single
‐alkene
isomer,
and
leverages
an
inexpensive
operationally
convenient
I(I)/I(III)
catalysis
platform.
first
example
catalytic
1,4‐difluorination
is
disclosed
subsequently
evolved
enable
1,4‐hetero‐difunctionalization,
which
δ‐fluoro‐alcohol
amine
derivatives
forged
in
operation.
protocol
compatible
with
variety
nucleophiles
including
fluoride,
nitriles,
carboxylic
acids,
alcohols
even
water
thereby
allowing
products,
stereocenter
bearing
both
C(sp
3
)−F
)−CF
groups,
generated
rapidly.
Scalability
(up
mmol),
facile
post‐reaction
modifications
are
demonstrated
underscore
the
utility
method
expanding
organofluorine
chemical
space.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(17), С. 12167 - 12173
Опубликована: Апрель 16, 2024
Harnessing
the
acidity
of
HF/base
reagents
is
paramount
importance
to
improve
efficiency
and
selectivity
fluorination
reactions.
Yet,
no
general
method
has
been
reported
evaluate
their
acidic
properties,
experimental
designs
are
still
relying
on
a
trial-and-error
approach.
We
report
new
based
