Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(38)
Published: Aug. 3, 2023
Abstract
Aliphatic
trifluoromethyl
ketones
are
a
type
of
unique
fluorine‐containing
subunit
which
play
significant
role
in
altering
the
physical
and
biological
properties
molecules.
Catalytic
methods
to
provide
direct
access
aliphatic
highly
desirable
yet
remain
underdeveloped,
partially
owing
high
reactivity
instability
trifluoroacetyl
radical.
Herein,
we
report
photocatalytic
synthesis
from
alkyl
bromides
with
trifluoroacetic
anhydride.
The
reaction
features
dual
visible‐light
halogen‐atom‐transfer
catalysis,
followed
by
an
enabling
radical‐radical
cross‐coupling
radical
stabilized
provides
straightforward
readily
available
cost‐effective
halides
anhydride
(TFAA).
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(37), P. 5587 - 5590
Published: Jan. 1, 2023
The
construction
of
diaryl
alkanes
from
aromatic
aldehydes
or
ketones
with
electron-deficient
arenes
is
achieved
in
the
presence
trivalent
phosphine
under
electrochemical
conditions.
Reductive
coupling
between
and
carbonyl
groups
occurs
at
cathode
to
yield
alcohols.
At
anode,
reagent
may
undergo
single-electron
oxidation
generate
its
radical
cation,
which
reacts
alcohols
form
dehydroxylated
products.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(21), P. 8385 - 8410
Published: Jan. 1, 2023
In
this
review,
8-aminoquinoline,
8-hydroxyquinoline,
and
1-naphthylamine
scaffolds
are
classified,
the
constructions
of
their
selective
C–H
activation
systems
reviewed
in
terms
photocatalytic
electrocatalytic
synthesis.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(85), P. 12763 - 12766
Published: Jan. 1, 2023
The
metal-free
alkylation
of
N-heterocycles
with
alkenes
has
remained
a
synthetic
challenge.
We
report
here
the
successful
implementation
quinoxalinones
electron-deficient
enabled
by
sequential
paired
electrolysis.
This
protocol
provides
mechanistically
distinct
approach
to
prepare
variety
C-3
alkylated
that
are
otherwise
quite
difficult
synthesize
other
means.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(35), P. 7408 - 7413
Published: Aug. 26, 2024
A
redox-neutral
coupling
of
allyl
alcohols
with
trifluoromethyl
ketones
has
been
developed
via
Ni–Ti
bimetallic
catalysis.
This
innovative
method
allows
for
the
efficient
synthesis
various
β-tertiary
alcohol-substituted
yields
up
to
98%.
The
reaction
is
scalable
and
compatible
a
wide
range
substrates,
including
complex
bioactive
molecules.
Mechanistic
studies
suggest
that
rate-determining
step
involving
β-H
elimination
presence
Ti-based
Lewis
acid,
as
well
hydroxyl
group
on
crucial
driving
reactivity
this
transformation.
Abstract
Classical
methods
for
the
synthesis
of
tertiary
alcohols
mainly
rely
on
nucleophilic
addition
organometallic
reagents
to
carbonyl
compounds.
Here,
we
disclose
a
strategy
synthesizing
via
electroreductive
cross‐electrophile
coupling
aromatic
compounds
and
alkyl
bromides
(allyl,
propargyl,
benzyl
cyclohexyl
bromides).
This
procedure
features
good
substrate
tolerance
friendly
conditions
(undivided
cell,
cheap
reusable
carbon
electrodes,
reaction
in
open
air,
room
temperature,
without
any
external
transition
metal/activating
reagent).
Using
this
method,
32
desired
products
can
be
obtained
with
moderate
yields,
gram‐scale
is
feasible,
demonstrating
practicality
approach.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 17, 2024
A
photocatalysis-involved
α-amino
radical
provides
an
appealing
approach
for
rapid
construction
of
complex
amine
architectures.
Reported
herein
is
organophotoredox
catalytic
to
α-C-H
alkylation
and
heteroarylation
benzyl
anilines,
which
enables
the
introduction
valuable
trifluoromethyl
alcohol,
chromanone,
or
pyridine
motifs
at
α
position
amines.
This
protocol
highlights
metal-free,
step
atom
economies
broad
substrate
scopes
(>80
examples).
Control
experiments
electron
paramagnetic
resonance
spectroscopy
identified
derived
from
C-H
bond.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(20), P. 4304 - 4308
Published: Jan. 1, 2023
An
efficient
catalyst-free
C(sp3)-H
bond
functionalization
of
methyl
azaarenes
with
heteroaromatic
trifluoromethyl
ketone
hydrates
in
neat
water
has
been
developed
for
the
synthesis
α-trifluoromethyl
tertiary
alcohols
bearing
N-heteroaromatics.
This
method
not
only
features
excellent
efficiency,
broad
substrate
scope,
conditions,
and
easy
gram-scale
preparation
but
also
represents
a
new
rare
example
"all-water"
trifluoromethylated
molecules.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(23), P. 3275 - 3280
Published: July 27, 2023
Comprehensive
Summary
α‐Fluoroalkyl
(R
f
)
alcohols
are
privileged
motifs
in
drugs
and
pharmaceutically
active
compounds.
As
such,
it
is
highly
desirable
to
develop
efficient
methods
for
assembling
these
scaffolds.
Herein,
a
visible‐light‐induced
cascade
radical
cyclization
of
alkenyl
fluoroalkyl
ketones
developed,
producing
variety
decorate
α‐R
cycloalkanols
promising
yields
with
up
>20
:
1
dr
selectivity.
A
chain
mechanism
involving
an
intramolecular
addition
the
carbonyl
group
subsequent
intermolecular
hydrogen
atom
transfer
(HAT)
has
been
proposed.
Density
functional
theory
(DFT)
calculations
indicate
that
fluorine
effect
contributes
carbonyls
by
lowering
π*
(C=O)
orbital
energy
COR
barrier
HAT
between
alkoxy
radicals
THF,
which
may
be
valuable
controllable
transformations
fluorinated
molecules.
