Chemistry - A European Journal,
Год журнала:
2020,
Номер
26(67), С. 15378 - 15396
Опубликована: Авг. 12, 2020
Abstract
Remote
functionalization
reactions
have
the
power
to
transform
a
C−H
(or
C−C)
bond
at
distant
position
from
functional
group.
This
Review
summarizes
recent
advances
and
key
breakthroughs
in
remote
fluorination,
trifluoromethylation,
difluoromethylation,
trifluoromethylthiolation,
fluoroalkenylation
reactions.
Several
powerful
strategies
emerged
control
reactivity
distal
selectivity
such
as
undirected
radical
approach,
1,5‐hydrogen
atom
transfer,
metal
migration,
use
of
directing
groups,
ring‐opening
These
unconventional
predictable
(and
transformations
should
allow
for
preparation
wide
range
otherwise‐difficult‐to‐access
alkyl,
aromatic,
heteroaromatic,
structurally
complex
fluorides.
Organic Letters,
Год журнала:
2021,
Номер
23(15), С. 5729 - 5733
Опубликована: Июль 14, 2021
A
broadly
applicable
method
for
the
trifluoromethylthiolation
of
methylene
C(sp3)–H,
methine
α-oxygen
and
formyl
C(sp2)–H
bonds
is
presented
using
decatungstate
anion
as
sole
catalyst.
By
adjusting
substrate
ratio
reaction
concentration,
this
was
applied
to
40
examples
in
good
regioselectivities,
including
derivatization
natural
products.
Furthermore,
SCF3–drug
analogues
were
synthesized
by
subsequent
functionalization
SCF3
products,
highlighting
importance
photocatalyzed
C–H
functionalization.
Organic Letters,
Год журнала:
2022,
Номер
24(3), С. 944 - 948
Опубликована: Янв. 20, 2022
A
method
of
N-fluorocarboxamide-directed
N-heterocyclic-carbene
(NHC)-catalyzed
benzylic
C-H
acylation
with
aldehydes
via
the
hydrogen
atom
transfer
strategy
is
disclosed.
This
transformation
involves
a
sequence
single-electron
transfer,
1,5-hydrogen
and
radical
cross-coupling
steps.
offers
facile
access
to
various
highly
functionalized
ketones
exhibits
good
chemical
yields
functional
group
tolerance.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3115 - 3127
Опубликована: Фев. 13, 2024
Although
the
transition
metal-catalyzed
radical
fluorine
atom
transfer
(FAT)
strategy
has
emerged
as
a
powerful
tool
for
construction
of
C–F
bonds,
to
our
knowledge,
this
approach
rarely
been
applied
formation
S–F
bonds.
Here,
we
report
that
4-methoxypyridine
1-oxide
can
serve
an
inexpensive
and
simple
yet
effective
ligand
thus
promote
transformation
copper-mediated
challengeable
FAT
sulfonyl
radicals,
paving
way
assembly
FSO2
group.
Based
on
concept,
three
Cu(I)-catalyzed
protocols
involving
site-selective
intra-
intermolecular
fluorosulfonylation
inert
C(sp3)–H
bonds
1,2-aminofluorosulfonylation
inactivated
alkenes
have
developed,
enabling
preparation
C(sp3)-rich
aliphatic
fluorides
cannot
be
easily
synthesized
by
known
methods.
These
practical
operationally
methods
result
in
high
functional
group
tolerance
under
mild
conditions
modification
bioactive
derivatives
highly
valued
molecules.
Detailed
mechanistic
studies
indicate
unique
role
facilitating
such
rare
FATs
via
outer-sphere
pathway.
Abstract
The
chemical
and
biological
interest
in
this
element
the
molecules
bearing
selenium
has
been
exponentially
growing
over
years.
Selenium,
formerly
designated
as
a
toxin,
becomes
vital
trace
for
life
that
appears
selenocysteine
its
dimeric
form,
selenocystine,
active
sites
of
selenoproteins,
which
catalyze
wide
variety
reactions,
including
detoxification
reactive
oxygen
species
modulation
redox
activities.
From
point
view
drug
developments,
organoselenium
drugs
are
isosteres
sulfur‐containing
oxygen‐containing
with
advantage
presence
atom
confers
antioxidant
properties
high
lipophilicity,
would
increase
cell
membrane
permeation
leading
to
better
oral
bioavailability.
This
statement
is
paramount
relevance
considering
big
number
clinically
employed
compounds
sulfur
or
atoms
their
structures
nucleosides
carbohydrates.
Thus,
article
we
have
focused
on
relevant
features
application
medicinal
chemistry.
With
increasing
chemistry,
attempted
highlight
most
significant
published
data
subject,
mainly
concentrating
analysis
last
In
consequence,
recent
advances
pharmacological
discussed.
Chemical Science,
Год журнала:
2019,
Номер
11(5), С. 1276 - 1282
Опубликована: Дек. 6, 2019
A
copper-catalyzed
site-selective
thiolation
of
Csp3–H
bonds
aliphatic
amines
was
developed.
The
method
features
a
broad
substrate
scope
and
good
functional
group
tolerance.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(7), С. 1835 - 1854
Опубликована: Фев. 25, 2021
Abstract
The
introduction
of
trifluoromethylchalcogen
group
(CF
3
O,
CF
S
and
Se)
has
attracted
growing
attention
in
the
field
modern
organofluorine
chemistry.
Compared
with
O
chemistry,
methods
for
trifluoromethylselenolation
are
much
less
developed
owing
to
limited
availability
Se
transfer
reagents
synthetic
methods.
introduces
promising
lipophilicity
(Hansch‐Leo
parameter=1.29)
strong
electron‐withdrawing
effect
(Hammett
constants
σ
m
=0.44,
p
=0.45)
which
important
parameters
development
new
pharmaceutically
relevant
compounds.
Traditionally,
compounds
were
synthesized
by
nucleophilic
trifluoromethylation
diselenides
selenocyanates,
suffered
from
harsh
conditions
and/or
substrates
scope.
indirect
methods,
direct
formation
C−SeCF
constitutes
is
a
more
efficient
approach.
In
recent
years,
enabled
incorporation
trifluoromethylselenyl
directly
under
mild
conditions,
specifically
transition
metal
catalysis
photoredox
catalysis.
this
review,
we
will
focus
on
strategies
based
magnified
image
Organic Letters,
Год журнала:
2020,
Номер
22(9), С. 3601 - 3606
Опубликована: Апрель 20, 2020
A
redox
neutral
radical-relay
cobalt-catalyzed
intramolecular
C–H
fluorination
of
N-fluoroamides
featuring
the
in
situ
formed
cobalt
fluorides
as
latent
radical
fluorinating
agents
is
reported.
Moreover,
reactivity
such
a
catalysis
could
be
diverted
from
to
amination
by
engineering
substrates'
conformational
flexibility.
Preliminary
mechanistic
studies
(UV–vis
spectroscopy,
cyclic
voltammetry
and
DFT
calculations,
etc.)
support
reaction
proceeding
mechanism.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(34), С. 18645 - 18650
Опубликована: Июнь 11, 2021
Site-selective
incorporation
of
deuterium
into
biologically
active
compounds
is
high
interest
in
pharmaceutical
industry.
We
present
a
mild
and
environmentally
benign
metal-free
method
for
the
remote
selective
radical
C-H
monodeuteration
aliphatic
bonds
various
amides
with
inexpensive
heavy
water
(D2
O)
as
source.
The
uses
easily
installed
N-allylsulfonyl
moiety
an
N-radical
precursor
that
generates
C-radical
via
site-selective
1,5-
or
1,6-hydrogen
atom
transfer
(HAT).
Methyl
thioglycolate,
readily
exchanges
its
proton
D2
O,
serves
deuteration
reagent
chain-carrier.
highly
has
been
applied
to
different
types
unactivated
sp3
-C-H
also
next
heteroatoms.
potential
utility
this
further
demonstrated
by
natural
product
derivatives
drugs.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(14), С. 3507 - 3520
Опубликована: Май 19, 2021
A
catalyst-
and
additive-free
decarbonylative
trifluoromethylthiolation
of
aldehyde
feedstocks
has
been
developed.
This
operationally
simple,
scalable,
open-to-air
transformation
is
driven
by
the
selective
photoexcitation
electron
donor-acceptor
(EDA)
complexes,
stemming
from
association
1,4-dihydropyridines
(donor)
with
N-(trifluoromethylthio)phthalimide
(acceptor),
to
trigger
intermolecular
single-electron
transfer
events
under
ambient-
visible
light-promoted
conditions.
Extension
other
acceptors
enables
synthesis
thiocyanates
thioesters,
as
well
difunctionalization
[1.1.1]
propellane.
The
mechanistic
intricacies
this
photochemical
paradigm
are
elucidated
through
a
combination
experimental
efforts
high-level
quantum
mechanical
calculations
[dispersion-corrected
(U)DFT,
DLPNO-CCSD(T),
TD-DFT].
comprehensive
study
highlights
necessity
for
EDA
complexation
efficient
alkyl
radical
generation.
Computation
subsequent
ground
state
pathways
reveals
that
SH2
addition
intermediate
complex
extremely
exergonic
results
in
charge
event
dihydropyridine
donor
acceptor
complex.
Experimental
computational
further
suggest
product
formation
also
occurs
via
reaction
radicals
1,2-bis(trifluoromethyl)disulfane,
generated
in-situ
thiyl
radicals.