Organic Letters,
Год журнала:
2022,
Номер
24(17), С. 3194 - 3198
Опубликована: Апрель 25, 2022
The
development
of
mild
and
practical
conditions
for
the
fluoroalkylation
arenes
is
an
ongoing
challenge
in
chemical
organic
synthesis.
Herein,
we
report
a
metallaphotoredox
method
preparation
fluoroalkyl
based
on
synergistic
combination
Ir/Cu
dual
catalysis
from
boronic
acids.
allow
broad
functional
group
tolerance,
including
substrates
containing
aldehydes,
free
phenols,
N-Boc-protected
amines.
Mechanistic
investigations
support
process
proceeding
via
photoredox/copper
catalysis.
Asian Journal of Organic Chemistry,
Год журнала:
2021,
Номер
10(4), С. 711 - 748
Опубликована: Фев. 11, 2021
Abstract
Photocatalyzed
organic
synthesis
transformation
is
a
remarkable
green
synthetic
strategy
because
of
the
advantages
operational
simplicity,
high
chemoselectivities,
cheap,
and
environmental
benignancy,
along
with
extensive
applications
in
fields
organic,
pharmaceutical
functional
material
chemistry.
Generally,
photoredox
catalysts
or
photosensitizers
are
necessary
for
generation
their
excited
states
to
perform
successive
oxidative
reductive
reactions
through
single
electron
transfer
(SET)
energy
(ET)
process.
Furthermore,
exploration
colored
donor‐acceptor
(EDA)
complex
charge
(CT)
between
an
electron‐rich
electron‐poor
substrate
provides
chance
deliver
intermediate
under
irradiation
light,
resulting
formation
radical
activate
species
induce
various
reactions.
These
were
performed
without
need
any
external
photocatalysts
mild
reaction
conditions.
Herein,
this
review
focuses
on
recent
progress
photoinduced
addition
reactions,
borylations,
radical‐radical
cross‐coupling
degradation
cascade
cyclization
via
EDA
complexes.
We
highlight
these
novel
methodologies
applications,
as
well
mechanisms.
This
will
help
provide
references
medicinal
chemists
who
charmed
by
photochemical
transformations
based
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(16), С. 10555 - 10563
Опубликована: Июль 29, 2022
Electron
donor–acceptor
(EDA)
complexes
provide
a
means
to
initiate
radical
reactions
under
visible
light
irradiation
using
substrates
that
do
not
absorb
individually.
Catalytic
approaches
complex
formation
are
vital
for
advancing
this
synthetic
strategy
as
it
decouples
the
complexation
and
photogeneration
of
radicals
from
substrate
functionalization,
limitation
inherent
stoichiometric
restricts
structural
diversity.
This
Synopsis
highlights
recent
developments
in
EDA
photochemistry
which
either
donor
or
acceptor
employed
catalytically.
Chemical Science,
Год журнала:
2023,
Номер
14(21), С. 5545 - 5568
Опубликована: Янв. 1, 2023
This
review
provides
a
comprehensive
overview
on
examples
of
how
photochemical
excitation
halogen-bonding
complexes
can
be
useful
for
the
generation
carbon-centered
radicals
and
their
participation
in
synthetic
organic
transformations.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Янв. 29, 2024
Abstract
We
highlight
key
contributions
in
the
field
of
direct
radical
C
Ar
−
H
(hetero)aromatic
functionalization
involving
fluorinated
radicals.
A
compilation
Functional
Group
Transfer
Reagents
and
their
diverse
activation
mechanisms
leading
to
release
radicals
are
discussed.
The
substrate
scope
for
each
is
analyzed
classified
into
three
categories
according
electronic
properties
substrates.
Density
functional
theory
computational
analysis
provides
insights
chemical
reactivity
several
through
electrophilicity
nucleophilicity
parameters.
Theoretical
reduction
potentials
also
highlights
remarkable
correlation
between
oxidizing
ability.
It
established
that
highly
(e.g.
⋅OCF
3
)
capable
engaging
single‐electron
transfer
(SET)
processes
rather
than
addition,
which
good
agreement
with
experimental
literature
data.
scale,
based
on
barrier
addition
these
benzene
elaborated
using
high
accuracy
DLPNO‐(U)CCSD(T)
method.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(15), С. 8275 - 8284
Опубликована: Апрель 5, 2023
Allyl
carboxylates
are
useful
synthetic
intermediates
in
a
variety
of
organic
transformations,
including
catalytic
nucleophilic/electrophilic
allylic
substitution
reactions
and
1,2-difunctionalization
reactions.
However,
the
1,3-difunctionalization
allyl
remains
elusive.
Herein,
we
report
first
photoinduced,
phosphine-catalyzed
1,3-carbobromination
carboxylates,
affording
range
valuable
substituted
isopropyl
(sIPC).
The
transformation
has
broad
functional
group
tolerance,
is
amenable
to
late-stage
modification
complex
molecules
gram-scale
synthesis,
expands
reaction
profiles
phosphine
catalysis.
Preliminary
experimental
computational
studies
suggest
non-chain-radical
mechanism
involving
formation
an
electron
donor-acceptor
complex,
1,2-radical
migration
(RaM),
Br-atom
transfer
processes.
We
anticipate
that
1,2-RaM
reactivity
radical
will
both
serve
as
platform
for
development
new
transformations
synthesis.
Chemical Communications,
Год журнала:
2023,
Номер
59(11), С. 1434 - 1448
Опубликована: Янв. 1, 2023
The
site-selective
modification
of
amino
acids,
peptides,
and
proteins
has
always
been
an
intensive
topic
in
organic
synthesis,
medicinal
chemistry,
chemical
biology
due
to
the
vital
role
acids
life.
Among
developed
methods,
introduction
fluorine
functionalities
into
peptides
emerged
as
a
useful
approach
change
their
physicochemical
biological
properties.
With
increasing
demand
for
life
science,
direct
fluorination/fluoroalkylation
also
received
attention
because
unique
properties
atom(s)
that
can
protein
structure,
increase
lipophilicity,
enable
functionality
tracer
or
probe
studies.
In
this
feature
article,
we
summarized
recent
advances
synthesis
fluorinated
wherein
two
strategies
have
discussed.
One
is
based
on
building
blocks
prepare
with
diversified
structures,
including
transformations
imines
nickel-catalyzed
dicarbofunctionalization
alkenes
bromodifluoroacetate
its
derivatives;
other
fluorination/fluoroakylation
proteins,
which
selective
functional
groups
serine,
threonine,
tyrosine,
tryptophan,
cysteine
lead
wide
range
α-amino
featuring
synthetic
convenience
late-stage
biomacromolecules.
These
complement
each
other,
transition-metal
catalysis
new
fluoroalkylating
reagents
provide
powerful
tools
selectively
access
showing
prospect
chemistry
biology.
Chemical Science,
Год журнала:
2023,
Номер
14(13), С. 3470 - 3481
Опубликована: Янв. 1, 2023
Recently,
photochemistry
of
Electron
Donor-Acceptor
(EDA)
complexes
employing
catalytic
amounts
electron
donors
have
become
interest
as
a
new
methodology
in
the
catalysis
field,
allowing
for
decoupling
transfer
(ET)
from
bond-forming
event.
However,
examples
practical
EDA
systems
regime
remain
scarce,
and
their
mechanism
is
not
yet
well-understood.
Herein,
we
report
discovery
an
complex
between
triarylamines
α-perfluorosulfonylpropiophenone
reagents,
catalyzing
C-H
perfluoroalkylation
arenes
heteroarenes
under
visible
light
irradiation
pH-
redox-neutral
conditions.
We
elucidate
this
reaction
using
detailed
photophysical
characterization
complex,
resulting
triarylamine
radical
cation,
its
turnover
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Фев. 7, 2024
Abstract
Light‐mediated
processes
have
received
significant
attention,
since
they
re‐surfaced
unconventional
reactivity
platforms,
complementary
to
conventional
polar
chemistry.
γ‐Lactones
and
cyclopropanes
are
prevalent
moieties,
found
in
numerous
natural
products
pharmaceuticals.
Among
various
methods
for
their
synthesis,
light‐mediated
protocols
coming
the
spotlight,
although
these
contingent
upon
use
of
photoorgano‐
or
metal‐based
catalysts.
Herein,
we
introduce
a
novel
photochemical
activation
iodo‐reagents
via
cheap
sodium
ascorbate
ascorbic
acid
enable
homolytic
scission
addition
onto
double
bonds.
The
developed
protocol
was
applied
successfully
formal
[3+2]
cycloaddition
synthesis
γ‐lactones,
traditional
atom
transfer
radical
(ATRA)
reactions
one‐pot
two‐step
conversion
alkenes
cyclopropanes.
In
all
cases,
desired
were
obtained
good
high
yields,
while
reaction
mechanism
thoroughly
investigated.
Depending
on
nature
iodo‐reagent,
halogen
hydrogen‐bonded
complex
is
formed,
which
initiates
process.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(12), С. 2912 - 2968
Опубликована: Фев. 5, 2021
Abstract
For
almost
40
years,
difluoromethylene
phosphonates
have
proven
to
be
versatile
molecular
tools
in
biochemical
studies
owing
their
close
resemblance
naturally
occurring
phosphates
and
phosphonates.
As
bioisosteric,
non‐hydrolyzable
analogs
of
these
essential
molecules,
can
target
the
critical
parts
cellular
machinery
therefore
exhibit
a
diverse
spectrum
biological
activity.
In
past
ten
there
appeared
many
new
methods
for
synthesis
Most
notably,
photoredox
catalysis
has
firmly
entered
field,
while
cross‐coupling
nucleophilic
strategies
met
considerable
elaboration
refinement,
entirely
accord
with
current
trends
synthetic
organic
chemistry.
Herein,
we
introduce
as
distinct,
high‐tech
subclass
resulting
from
research
efforts
on
cross‐section
organophosphorus,
organofluorine,
bioorganic
We
then
proceed
discussion
general
preparation
phosphonates,
comprehensively
reviewing
reactions
developed
15
years
providing
context
earlier
works
where
appropriate.
Finally,
present
selected
examples
molecules
high
activity,
targets,
steps
employed
preparation.
magnified
image
