Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(62)
Published: Aug. 12, 2023
A
novel
one-pot
two-step
multicomponent
reaction
has
been
achieved
for
the
preparation
of
β-CF3
enamines
by
using
different
aliphatic
amines,
propiolates,
and
CF3
SO2
Na
as
starting
material.
In
this
protocol,
various
amines
including
primary
cyclic
or
acyclic
secondary
were
demonstrated
to
be
good
coupling
partners,
obtained
in
moderate
yields.
Among
them,
only
gave
pure
(E)-β-CF3
products.
The
synthetic
utility
MCRs
strategy
was
further
mild
conditions,
gram-scale
synthesis
natural
sunlight-induced
protocol.
Preliminary
mechanistic
studies
suggest
that
trifluoromethylation
C(sp2
)-H
involves
radical
process.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(8), P. 2195 - 2200
Published: Jan. 1, 2024
A
Heck-like
coupling
of
cyclic
sulfonium
salts
with
alkenes
via
selective
C–S
bond
cleavage
using
a
copper
complex
as
photosensitizer
through
visible-light-driven
redox-neutral
process
has
been
developed.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(10), P. 1678 - 1682
Published: March 3, 2023
The
electrochemical
difluoromethylation
of
electron-rich
olefins
(enamides
and
styrene
derivatives)
is
disclosed.
addition
the
electrogenerated
difluoromethyl
radical
from
corresponding
sodium
sulfinate
(i.e.,
HCF2SO2Na)
to
enamides
styrenes
in
an
undivided
cell
allowed
formation
a
large
panel
difluoromethylated
building
blocks
good
excellent
yields
(42
examples,
23-87%
yields).
A
plausible
unified
mechanism
was
suggested
according
control
experiments
cyclic
voltammetry
measurements.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(16), P. 11001 - 11011
Published: Aug. 4, 2023
The
radical
1,2-difunctionalization
reaction
of
alkynes
has
evolved
into
a
versatile
approach
to
multisubstituted
alkylenes.
However,
robust
catalytic
strategies
perform
carboamination
are
lacking,
despite
the
ubiquity
resulting
enamines
in
natural
molecules,
bioactive
and
pharmaceutical
compounds.
Herein,
we
show
that
bidentate
coordinating
group
judiciously
installed
on
amines
could
act
as
an
efficient
tool
for
enabling
trifluoromethylamidation
alkynes.
This
strategy
exhibits
broad
substrate
scope
with
good
functional
compatibility
is
amenable
late-stage
functionalization
compounds
biologically
relevant
motifs,
allowing
straightforward
synthesis
large
library
CF3-containing
enamides,
high-value
pharmacophores,
single
step
from
readily
accessible
amides,
Langlois'
reagent,
current
methodology
can
also
be
successfully
extended
difluoromethylamidation
Additionally,
various
mechanistic
experiments,
such
competition
H/D
isotopic
exchanging
trap
Hammett
studies,
kinetic
have
been
performed
better
understanding
mechanism.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
89(1), P. 216 - 223
Published: Dec. 18, 2023
The
C–N
bond
transamidation
of
primary
amides
with
N,N-dimethyl
enaminones
has
been
efficiently
realized
by
heating
in
the
presence
trifluoromethanesulfonic
acid
(TfOH).
method
enables
practical
synthesis
valuable
enamides
without
use
any
metal
reagent.
In
addition,
this
protocol
can
also
be
expanded
to
reactions
sulfonamides,
and
late-stage
functionalization
on
sulfonamide
drugs
such
as
Celecoxib
Valdecoxib
verified.
Moreover,
participation
water
assisting
process
identified
isotope
labeling
experiments
using
D2O,
disclosing
a
new
possibility
designing
catalytic
tactic
other
reactions.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(13), P. 2919 - 2925
Published: March 2, 2024
Abstract
A
regioselective
electrochemical
oxytrifluoromethylation
of
endocyclic
enamides
is
reported.
The
1,2‐difunctionalization
proceeds
under
mild
conditions
and
employs
the
inexpensive
bench
stable
Langlois’
reagent.
This
multicomponent
strategy
gives
access
to
a
wide
range
α,β‐substituted
amines
by
means
various
alcohols
as
nucleophiles
in
high
yields
with
good
functional
group
tolerance.
In
addition,
an
electrochemically
induced
C−H
trifluoromethylation
has
been
developed.
continuous
flow
protocol
using
commercial
microflow
reactor
was
also
developed
improved
reaction
performance
efficiency
over
traditional
batch
versions
without
any
supporting
electrolyte.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(17), P. 3673 - 3678
Published: April 19, 2024
Herein,
rhodium(III)-catalyzed
β-C(sp2)–H
alkenylation
and
alkylation
of
enamides
are
presented
using
readily
accessible
allylic
alcohols
by
switching
the
reaction
conditions.
This
tunable
transformation
has
been
applied
to
a
wide
range
substrates
typically
proceeded
with
excellent
regioselectivity
stereoselectivity
as
well
good
functional
group
tolerance.
The
catalytic
system
offers
an
efficient
approach
for
synthesizing
various
functionalized
bearing
N-(2Z,4E)-butadiene
(Z)-β-C(sp2)–H
alkylated
enamides.
In
addition,
mechanistic
experiments
suggest
that
Rh(III)-catalyzed
C–H
activation
is
not
related
critical
step.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(3), P. 954 - 1014
Published: Dec. 14, 2023
The
review
summarises
various
photo-
and
electrochemical
strategies
for
trifluoromethylation
fluoroalkylation
of
different
C(sp
3
)–H,
2
C(sp)–H
bonds
in
several
classes
organic
molecules.
