Abstract
This
review
describes
the
main
advances
in
enantioselective
fluorination
over
last
decade,
while
also
recalling
early
developments
this
area.
Three
strategies
have
been
employed
to
achieve
concomitant
introduction
of
a
fluorine
atom
by
C(sp3)—F
bond
formation
with
stereocon-trol
at
same
carbon
center:
(1)
use
chiral
fluorinating
agents,
(2)
diverse
organocatalytic
approaches,
and
(3)
transition-metal-catalyzed
fluorinations.
These
complementary
ap-ply
both
electrophilic
nucleophilic
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8270 - 8293
Опубликована: Май 13, 2024
As
one
of
the
most
important
key
intermediates,
NHC-bound
acylazolium-based
ionic
transformations
have
been
intensively
explored
in
past
two
decades.
With
expeditious
development
NHC-catalyzed
radical
recent
years,
acylazolium
chemistry
has
reached
another
level,
with
number
relevant
publications
increasing
significantly.
However,
a
summary
focused
on
acylations
NHC-derived
acyl
azoliums
classified
according
to
mechanistic
difference
not
reported.
Such
detailed
classification
and
deep
analysis
provide
opportunities
for
better
understanding
history
trend
this
field.
In
review,
reactions
N-heterocyclic
carbene
(NHC)-derived
are
systematically
introduced.
The
achievements
challenges
within
area
also
summarized
discussed
at
end.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 25, 2025
Comprehensive
Summary
Vicinal
all‐carbon
quaternary
stereocenters
are
widely
present
in
natural
products
and
bioactive
molecules.
However,
the
construction
of
such
motif
one
step
from
readily
available
starting
materials
remains
a
significant
challenge.
Herein,
we
report
phosphine‐catalyzed
divergent
γ,γ‐
ε,γ‐umpolung
domino
addition
bisoxindoles
with
allenoates.
This
method
serves
as
practical
tool
for
concise
synthesis
series
bisoxindole
derivatives
bearing
sterically
hindered
vicinal
under
mild
reaction
conditions.
The
applicability
this
novel
was
demonstrated
gram‐scale
three
known
advanced
intermediates
total
syntheses
calycanthine,
chimonanthine
folicanthine.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2762 - 2767
Опубликована: Янв. 1, 2024
A
P(NMe2)3-catalyzed
[4
+
2]
annulation
of
2-amino-β-nitrostyrenes
and
β′-acetoxy
allenoates
followed
by
a
Zn/AcOH-mediated
reduction–hydroamination–isomerization
has
been
developed.
Chemical Communications,
Год журнала:
2024,
Номер
60(53), С. 6773 - 6776
Опубликована: Янв. 1, 2024
A
novel
phosphine-mediated
α-umpolung/Wittig
olefination/cyclization
cascade
process
between
o
-aminobenzaldehydes
and
Morita–Baylis–Hillman
(MBH)
carbonates
has
been
ingeniously
developed
for
the
facile
synthesis
of
a
broad
range
2-vinylindolines.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(26)
Опубликована: Май 22, 2024
Abstract
Here
we
report
a
mild
protocol
for
benzylic
C−H
trifluoromethylthiolation
using
sodium
decatungstate
(NaDT)
as
the
photocatalyst.
Wherein,
photoactivated
DT
abstracted
hydrogen
atom
via
radical
process.
This
transformation
works
well
with
slight
excess
of
substrates
or
limiting
reagents
better
purification.
The
reaction
shows
conditions
and
good
functional
group
tolerance.
Moreover,
could
be
applied
to
gram‐scale
synthesis.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7790 - 7794
Опубликована: Май 29, 2024
The
incorporation
of
difluoromethylene
groups
into
aza-heterocycles
represents
a
compelling
yet
underexplored
avenue
in
contemporary
chemical
research.
In
this
study,
we
unveil
hybrid
palladium-catalyzed
intramolecular
gem-difluoroalkylamination
conjugated
dienes,
providing
versatile
approach
to
the
synthesis
diverse
functionalized
pyrrolidines.
Noteworthy
features
include
mild
reaction
conditions
and
remarkable
tolerance
toward
various
functional
groups.
Additionally,
use
alkyl
iodides
as
electrophiles
facilitates
generation
corresponding
alkylamination
products.
Control
experiments
support
proposed
radical–polar
crossover
pathway,
offering
insights
underlying
processes
governing
transformation.
We
disclose
herein
a
chiral
phosphoric-acid-catalyzed
enantioselective
addition
reaction
of
alcohols
to
fluoroalkylated
biaryl
1,3-oxoazepines,
which
furnished
wide
range
bridged
biaryls
bearing
quaternary
carbon
stereocenter
on
the
seven-membered
ring
in
high
yields
(up
99%)
with
excellent
enantioselectivities
98%
ee).
Our
method
can
be
used
for
modification
several
natural
products
and
bioactive
molecules.
Preliminary
studies
revealed
that
obtained
this
exhibit
good
vitro
bioactivities
against
two
plant
pathogens.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 7, 2025
Abstract
Enantioenriched
α
-chiral
β
-fluorinated
ketones
are
valuable
structural
motifs
with
application
in
several
fields.
The
recently
emerged
concept
of
NHC-catalyzed
radical
acyl-trifluoromethylation
olefins
offers
a
rapid
route
to
construct
racemic
single
step.
Due
the
lack
competent
chiral
NHC
catalysts
constructing
these
molecules
an
enantioselective
manner
remains
unmet
challenge.
Herein,
we
report
family
thiazolium
carbenes
having
bulky
flanking
groups
and
offering
three
distinct
positions
broad
steric
electronic
tunability.
display
so
far
unmatched
enantioselectivities
for
acyl-trifluoromethylations
simple
unactivated
wide
variety
aldehydes
Togni’s
reagent.
method
provides
enantioenriched
-trifluoromethylated
high
yields
excellent
up
98:2
er.
A
potential
applicability
this
methodology
is
demonstrated
through
enantio-
diastereoselective
late-stage
functionalizations
pharmaceutical
compounds.
Chemical Communications,
Год журнала:
2024,
Номер
60(71), С. 9483 - 9512
Опубликована: Янв. 1, 2024
This
review
highlights
recent
advances
in
transition
metal
complexes
of
silylene,
showcasing
their
efficacy
hydroboration,
hydrosilylation,
hydrogenation,
hydrogen
isotope
exchange,
and
small
molecule
activation
chemistry.
