Angewandte Chemie,
Год журнала:
2022,
Номер
134(46)
Опубликована: Авг. 26, 2022
Abstract
Stereochemically
defined
organofluorine
compounds
are
vital
to
drug
discovery
and
many
applicable
catalytic
strategies
have
been
introduced
for
accessing
these
entities
stereoselectively.
One
approach
entails
incorporation
of
a
fluorine
atom
(C−F
bond
formation)
or
an
moiety
(e.g.,
CF
3
2
H),
another
exploits
commercially
available
with
one
more
atoms.
Here,
we
present
the
state‐of‐the‐art
regarding
use
alkenyl
allylic
fluorides
in
preparation
stereochemically
fluoro‐organic
molecules.
Allylic
may
be
purchased
generated
from
acid,
carboxylate
salt,
ester,
aldehyde
hydrate,
ketone
bearing
several
atoms
next
carbonyl
group.
We
underscore
untapped
potential
purchasable
compounds,
fluorides,
as
launching
points
development
stereoselective
processes
that
value
therapeutic
science.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Organic Letters,
Год журнала:
2024,
Номер
26(6), С. 1201 - 1206
Опубликована: Фев. 3, 2024
We
developed
an
asymmetric
decarboxylative
allylic
alkylation
of
vinylethylene
carbonates
with
α-fluoro
pyridinyl
acetates
through
a
synergistic
palladium/copper
catalysis.
This
protocol
provides
chiral
alcohol
carbon–fluorine
quaternary
stereogenic
centers
in
good
yield
enantioselectivities
and
excellent
regioselectivities.
The
utility
this
approach
was
further
demonstrated
via
gram-scale
experiment
derivatizations
the
product.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(46)
Опубликована: Авг. 26, 2022
Stereochemically
defined
organofluorine
compounds
are
vital
to
drug
discovery
and
many
applicable
catalytic
strategies
have
been
introduced
for
accessing
these
entities
stereoselectively.
One
approach
entails
incorporation
of
a
fluorine
atom
(C-F
bond
formation)
or
an
moiety
(e.g.,
CF3
CF2
H),
another
exploits
commercially
available
with
one
more
atoms.
Here,
we
present
the
state-of-the-art
regarding
use
alkenyl
allylic
fluorides
in
preparation
stereochemically
fluoro-organic
molecules.
Allylic
may
be
purchased
generated
from
acid,
carboxylate
salt,
ester,
aldehyde
hydrate,
ketone
bearing
several
atoms
next
carbonyl
group.
We
underscore
untapped
potential
purchasable
compounds,
fluorides,
as
launching
points
development
stereoselective
processes
that
value
therapeutic
science.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(15), С. 3909 - 3928
Опубликована: Янв. 1, 2023
The
latest
achievements
in
transition-metal-catalyzed
enantioselective
defluorinative
coupling
reactions
have
been
comprehensively
summarized
on
the
basis
of
classification
transition-metal
catalysts.
ACS Catalysis,
Год журнала:
2023,
Номер
13(20), С. 13838 - 13845
Опубликована: Окт. 12, 2023
Despite
advances
in
the
field
of
asymmetric
catalysis,
synthesis
complete
sets
stereoisomers
multistereogenic
molecules,
particularly
those
incorporating
a
fluorine
atom,
remains
challenging
task.
We
report,
herein,
stereodivergent
method
for
tertiary
alkyl
fluorides
vicinal
stereogenic
pairs
through
conjugate
addition
α-fluoro
azaaryl
acetamides
to
α,β-unsaturated
aldehydes
catalyzed
by
combination
two
chiral
catalysts:
copper
Lewis
acid
and
an
amine.
This
process
occurs
synergistic
catalytic
cycle
which
reaction
between
situ-generated
iminium
α-azaaryl
α-fluoroenolate
intermediates
constructs
carbon–carbon
bond,
furnishing
array
4-fluorinated
1,5-aldehyde
amides
with
high
stereocontrol.
By
simply
varying
combinations
catalyst
enantiomers,
all
four
products
are
selectively
accessible.
Moreover,
can
be
further
derivatized
into
other
enantioenriched
fluorinated
some
contain
stereocenters
within
three
contiguous
stereocenters.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(23), С. 4592 - 4612
Опубликована: Янв. 1, 2024
Synthesis
of
fluorinated
quaternary
carbon
centers
by
a
series
asymmetric
alkylation,
arylation,
Mannich,
Michael
addition,
aldol,
and
allylation
reactions.
Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(2), С. 101822 - 101822
Опубликована: Фев. 1, 2024
Catalytic
asymmetric
alkylation
of
α-halogenated
enolates
is
a
challenging
issue
due
to
their
extenuated
nucleophilicity
and
the
electrophilic
oxidative
nature
parent
α-Cl/Br
carbonyl
compounds.
Herein,
by
means
coordination-stabilized
copper(I)
α-F/Cl
as
nucleophiles,
catalytic
2-azaarylesters
achieved
with
broad
substrate
scope
on
alkyl
halides,
which
constructs
halogenated
tetrasubstituted
carbon
centers
in
good
excellent
yields
high
enantioselectivity.
Moreover,
present
protocol
successfully
applied
building
chiral
quaternary
centers.
Finally,
synthetic
utilities
products
are
demonstrated
several
facile
transformations
based
chloride
group
ester
group.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(1), С. 142 - 148
Опубликована: Ноя. 22, 2023
A
direct
electrolysis
protocol
for
difluorination
and
azo-fluorination
of
gem
-difluorostyrenes
was
achieved
involving
Et
3
N·3HF
as
fluorine
source.
The
electrochemical
reduction
the
benzyl
C–F
bond
also
achieved.
Synthesis,
Год журнала:
2022,
Номер
54(23), С. 5168 - 5185
Опубликована: Авг. 25, 2022
Abstract
Chiral
sulfoxide
is
considered
to
be
an
ideal
candidate
ligand
for
transition-metal-catalyzed
asymmetric
reactions
due
its
ease
of
synthesis,
stability,
and
exceptional
S-stereological
orientation
control.
This
paper
reviews
the
different
types
asymmetrical
with
chiral
ligands
in
recent
years,
as
well
a
discussion
efficient
methods
preparation
some
enantiomerically
pure
sulfoxides.
1
Introduction
2
Sulfoxides
Ligands
Metal-Catalyzed
Asymmetric
Catalysis
3
Synthesis
4
Conclusions
Green Synthesis and Catalysis,
Год журнала:
2023,
Номер
5(1), С. 14 - 19
Опубликована: Янв. 13, 2023
A
novel
defluorinative
ring-opening
of
gem-difluorocyclopropenes
is
presented,
providing
a
concise
and
efficient
method
for
accessing
2-fluoropropenals
2-fluorobuta-1,3-dienes
in
moderate
to
good
yields
with
excellent
regio-
stereoselectivities.
The
reaction
performed
under
mild
conditions
no
need
using
an
excess
amount
nucleophilic
reagents.
Water
plays
crucial
role
this
transformation.
