ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 4053 - 4065
Published: March 1, 2024
Chiral
recognition
for
the
synthesis
of
axially
chiral
biaryl
units
is
a
fundamental
and
challenging
topic
in
organic
synthesis.
Herein,
we
documented
that
an
efficient
O-ligand
exchange
between
catalyst
substrate
enabled
axial
asymmetric
aminopalladation/olefination
2-alkynylanilides
vinyl
trifluoromethanesulfonates,
providing
3-alkenylindoles
with
up
to
97%
ee
98%
yield.
This
protocol
features
mild
conditions,
broad
functional
group
tolerance,
scalability,
late-stage
modification
bioactive
molecules.
Experimental
computational
studies
hinted
(R)-BIDIME/Pd
complex
alkoxy
was
crucial
success
stereoselectivity
control.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(4), P. 883 - 888
Published: Jan. 22, 2024
Herein,
we
present
a
transition-metal-free,
easy
handling
protocol
for
regioselective
carboxylation
of
gem-difluorostyrenes
with
sodium
formate
as
the
C1
source.
30
examples
α-fluoracrylates
were
obtained
in
yields
to
80%
under
these
conditions.
A
defluorinative
monofluorovinyl
intermediate
and
consecutive
photoinduced
electron
transfer
mechanism
proposed
after
investigation.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
gem-Difluorohomoallyl
amines,
an
important
class
of
gem-difluoroalkenes,
are
prevalent
moieties
in
many
bioactive
compounds.
However,
limited
methods
suitable
for
the
synthesis
this
type
compound
containing
secondary
amines.
Here,
we
display
a
photocatalytic
multicomponent
protocol
gem-difluoroalkenes
which
makes
use
readily
available
materials:
arylamines,
alkyl
aldehydes,
and
α-trifluoromethyl
alkenes.
Moreover,
ketones
amines
also
substrates.
Preliminary
mechanistic
experiments
indicate
that
key
α-amino
radical
was
involved,
generated
from
reduction
situ-formed
imines
(or
iminium
ions)
by
reduced
photocatalyst.
Subsequent
addition
to
alkenes
β-F
elimination
deliver
desired
products.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
summarizes
recent
advances
in
asymmetric
alkenyl
C–H
bond
functionalization
reactions,
as
well
provides
an
outlook
on
future
opportunities
and
challenges.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(40), P. 7298 - 7303
Published: Oct. 3, 2023
An
unprecedented
protocol
for
a
Rh(III)-catalyzed
[3
+
2]
annulation
from
simple
and
readily
available
enaminones
iodonium
ylides
has
been
developed.
The
novel
strategy
allows
access
to
new
class
of
structurally
diverse
tetrahydro-indolones
with
high
efficiency
broad
substrate
scope.
In
addition,
this
transformation
represents
the
first
example
selective
alkenyl
C–H
bond
functionalization
enaminones.
Finally,
potential
applications
are
demonstrated
through
gram-scale
reaction
late-stage
modification.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(18), P. 12238 - 12268
Published: Sept. 1, 2023
Organofluorine
compounds
have
attracted
extensive
attention
in
various
industrial
fields
due
to
their
unique
chemical
and
physical
properties.
Despite
increasing
demand
a
wide
range
of
scientific
fields,
the
synthesis
organofluorine
still
faces
several
problems,
such
as
difficulties
handling
fluorinating
reagents
control
chemoselectivity.
Compared
with
formation
C–F
bonds,
activation
functionalization
carbon–fluorine
bonds
is
very
important
but
challenging
topic
synthetic
chemistry.
Due
properties
nickel,
Ni-catalyzed
defluorinative
cross-couplings
been
greatly
developed
past
few
decades
powerful
strategies
for
construction
fluorinated
organic
compounds.
This
Review
summarizes
advances
cross-coupling
aryl
fluorides,
gem-difluorovinyl
trifluoromethyl
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(20)
Published: March 16, 2023
Monofluoroalkenes
are
nonhydrolyzable
mimetics
of
amides.
Previous
work
focused
on
the
synthesis
non-cyclic
monofluoroalkenes.
However,
diastereoselective
monofluorocyclohexenes
from
substrates
is
challenging.
Herein,
we
report
first
photocatalyzed
cascade
cyclization
reactions
readily
available
α,β-unsaturated
carbonyl
compounds
and
gem-difluoroalkenes
for
highly
functionalized
monofluorocyclohexenes.
The
reaction
shows
broad
substrate
scope
with
high
diastereoselectivity
(>30
examples,
up
to
86
%
yield,
>20
:
1
dr).
post-reaction
transformations
products
demonstrate
synthetic
potential
this
methodology.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4318 - 4342
Published: Jan. 1, 2024
This
review
primarily
focuses
on
the
generation
of
aryl
radicals
via
an
electroreduction
strategy,
and
systematically
elaborates
synthetic
applications,
scope,
limitations
substrates.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 31, 2024
Abstract
Introducing
distinctive
functional
groups
to
expand
the
structural
diversity
and
improve
intrinsic
properties
of
parent
molecules
has
been
an
essential
pursuit
in
organic
chemistry.
By
using
perfluoroalkyl
halide
(PFAH)
as
a
nontraditional,
readily
available,
ideal
1,2‐difluoroalkenyl
coupling
partner,
defluorinative
cyclization
reaction
enamides
for
construction
fluoroalkenyl
oxazoles
is
first
developed.
The
selective
controllable
two‐fold
cleavage
vicinal
C(sp
3
)─F
bonds
PFAH
not
only
enables
introduction
specific
moiety
with
ease
but
also
results
functionalization
two
2
)─H
without
need
metal
catalyst,
photocatalyst,
oxidant,
or
light.
method
can
be
applied
late‐stage
modification
complex
molecules,
synthesis
biological‐relevant
oxazole
analoges,
scale‐up
synthesis,
which
all
further
highlight
real‐world
utility
this
protocol.
Mechanistic
studies
reveal
that
possibly
proceeds
through
radical
perfluoroalkylation,
consecutive
C─F
bond
heterolytic
cleavage,
process.
In
addition,
situ
formed
may
serve
hydrogen
abstractor.
