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.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 3184 - 3190
Published: Feb. 6, 2025
A
direct
electroreductive
functionalization
of
tropones
employing
aldehydes
as
alkylating
agents
is
reported.
This
C(sp2)-H
process
leverages
the
mediation
electroactive
nickel
complexes,
enabling
a
wide
range
both
native
and
substituted
(44
examples)
to
be
alkylated
selectively
at
α-position
in
high
yields
(up
90%).
Combined
electrochemical,
spectroelectrochemical,
computational
analyses
disclosed
whole
mechanistic
pathway
revealed
key
role
played
by
reduced
Ni
complexes
activating
tropone
core
toward
condensation
with
aldehydes.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 20, 2025
The
trifluoroethoxy
group
(OCH2CF3)
is
a
valuable
motif
prevalent
in
pharmaceuticals
and
agrichemicals.
Herein,
we
present
simple
radical
trifluoroethoxylation
method
that
enables
nondirected
functionalization
of
C-H
bonds
broad
array
substrates,
providing
access
to
(hetero)aryl
trifluoroethyl
ethers.
current
protocol
tolerates
variety
synthetically
pharmacologically
relevant
functional
groups.
Applicability
also
demonstrated
through
the
late-stage
biorelevant
molecules
marketing
drugs.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Sept. 26, 2022
A
nickel-catalyzed
reductive
cross-electrophile
coupling
between
the
redox-active
N-trifluoroethoxyphthalimide
and
iodoarenes
is
documented.
The
protocol
reproduces
a
formal
arylation
of
trifluoroacetaldehyde
under
mild
conditions
in
high
yields
(up
to
88
%)
with
large
functional
group
tolerance
(30
examples).
combined
computational
experimental
investigation
revealed
pivotal
solvent
assisted
1,2-Hydrogen
Atom
Transfer
(HAT)
process
generate
nucleophilic
α-hydroxy-α-trifluoromethyl
C-centered
radical
for
Csp
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(18), P. 2664 - 2667
Published: Jan. 1, 2023
An
electrochemical
allylation/alkylation
of
cyclic/acyclic
ethers
is
presented
via
a
C(sp
3
)–H
activation,
proceeding
under
cathodic
reduction.
The
reaction
shows
broad
functional
group
tolerance
and
high
yields.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(18)
Published: Jan. 6, 2024
Hydroxytrifluoroethyl
and
trifluoroacetyl
groups
are
of
utmost
importance
in
biologically
active
compounds,
but
methods
to
tether
these
motifs
organic
architectures
have
been
limited.
Typically,
the
preparation
compounds
relied
on
use
strong
bases
or
multistep
routes.
The
renaissance
radical
chemistry
photocatalytic,
transition
metal
mediated,
hydrogen
atom
transfer
(HAT)
processes
allowed
installation
medicinally
relevant
fluorinated
motifs.
This
review
provides
an
overview
available
for
direct
synthesis
hydroxytrifluoroethyl-
trifluoroacetyl-derived
governed
by
single-electron
processes.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Oct. 6, 2023
The
cross-dehydrogenative
coupling
(CDC)
reaction
is
the
most
direct
and
efficient
method
for
constructing
α-tertiary
amino
acids
(ATAAs),
which
avoids
pre-activation
of
C(sp3)-H
substrates.
However,
use
transition
metals
harsh
conditions
are
still
significant
challenges
these
reactions
that
urgently
require
solutions.
This
paper
presents
a
mild,
metal-free
CDC
construction
ATAAs,
compatible
with
various
benzyl
C-H
substrates,
functionalized
alkyl
good
regioselectivity.
Notably,
our
exhibits
excellent
functional
group
tolerance
late-stage
applicability.
According
to
mechanistic
studies,
one-step
synthesized
bench-stable
N-alkoxyphtalimide
generates
highly
electrophilic
trifluoro
ethoxy
radical
serves
as
key
intermediate
in
process
acts
hydrogen
atom
transfer
reagent.
Therefore,
additive-free
offers
promising
strategy
synthesis
ATAAs
under
mild
conditions.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(18), P. 2203 - 2210
Published: May 14, 2024
Comprehensive
Summary
Compared
to
well‐established
1,5‐HAT
of
N
‐centered
radicals,
the
synthetic
applications
1,2‐HAT
process
were
scarce
due
high
barrier
and
constrained
three‐membered
transition
state.
Here,
we
have
developed
a
novel
C(sp
3
)‐H
gem
‐difluoroallylation
via
base
assisted
formal
amidyl
radicals
with
reductive
quenching
cycle
photocatalyst.
This
transformation
enables
efficient
formation
α‐aminoalkyl
showcases
good
functional
group
tolerance.
Our
preliminary
mechanistic
experiments,
along
Density
Functional
Theory
(DFT)
calculations
demonstrate
feasibility
especially
when
by
base.
Furthermore,
our
method
also
succeeds
in
Giese
addition
electron‐deficient
alkenes
as
well
styrene.
