Angewandte Chemie,
Год журнала:
2023,
Номер
135(46)
Опубликована: Окт. 2, 2023
Abstract
This
research
explores
the
enantioselective
hydrosulfonylation
of
various
α,β‐unsaturated
carbonyl
compounds
via
use
visible
light
and
redox‐active
chiral
Ni‐catalysis,
facilitating
synthesis
enantioenriched
α‐chiral
sulfones
with
remarkable
enantioselectivity
(exceeding
99
%
ee).
A
significant
challenge
entails
enhancing
reactivity
between
metal‐coordinated
moderate
electrophilic
sulfonyl
radicals,
aiming
to
minimize
background
reactions.
The
success
our
approach
stems
from
two
distinctive
attributes:
1)
Cl‐atom
abstraction
employed
for
radical
generation
chlorides,
2)
single‐electron
reduction
produce
a
key
enolate
Ni‐complex.
latter
process
appears
enhance
feasibility
radical's
addition
electron‐rich
radical.
An
in‐depth
investigation
into
reaction
mechanism,
supported
by
both
experimental
observations
theoretical
analysis,
offers
insight
intricate
process.
Moreover,
versatility
methodology
is
highlighted
through
its
successful
application
in
late‐stage
functionalization
complex
bioactive
molecules,
demonstrating
practicality
as
strategy
producing
sulfones.
Chemical Reviews,
Год журнала:
2023,
Номер
123(8), С. 4237 - 4352
Опубликована: Янв. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
aims
to
provide
an
overview
of
radical
Brook
rearrangement,
which
is
organized
by
grouping
three
type
reactive
species
generated
via
the
unique
rearrangement
process.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(66)
Опубликована: Сен. 6, 2022
Abstract
The
electrochemical
synthesis
of
fluorinated
allyl
silanes
and
boronates
was
disclosed.
addition
electrogenerated
boryl
or
silyl
radicals
onto
many
α‐trifluoromethyl
α‐difluoromethylstyrenes
in
an
undivided
cell
allowed
the
formation
a
large
panel
synthetically
useful
gem
‐difluoro
γ‐fluoroallyl
(64
examples,
from
31
%
to
95
yield).
In
addition,
scale
up
reactions
under
continuous
flow
showcased
using
reactor
with
promising
volumetric
productivity
(688
g.L
−1
.h
496
).
Moreover,
synthetic
utility
these
building
blocks
highlighted
through
versatile
transformations.
Finally,
plausible
reaction
mechanisms
were
suggested
explain
products.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(46)
Опубликована: Окт. 2, 2023
This
research
explores
the
enantioselective
hydrosulfonylation
of
various
α,β-unsaturated
carbonyl
compounds
via
use
visible
light
and
redox-active
chiral
Ni-catalysis,
facilitating
synthesis
enantioenriched
α-chiral
sulfones
with
remarkable
enantioselectivity
(exceeding
99
%
ee).
A
significant
challenge
entails
enhancing
reactivity
between
metal-coordinated
moderate
electrophilic
sulfonyl
radicals,
aiming
to
minimize
background
reactions.
The
success
our
approach
stems
from
two
distinctive
attributes:
1)
Cl-atom
abstraction
employed
for
radical
generation
chlorides,
2)
single-electron
reduction
produce
a
key
enolate
Ni-complex.
latter
process
appears
enhance
feasibility
radical's
addition
electron-rich
radical.
An
in-depth
investigation
into
reaction
mechanism,
supported
by
both
experimental
observations
theoretical
analysis,
offers
insight
intricate
process.
Moreover,
versatility
methodology
is
highlighted
through
its
successful
application
in
late-stage
functionalization
complex
bioactive
molecules,
demonstrating
practicality
as
strategy
producing
sulfones.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(14), С. 2299 - 2309
Опубликована: Июнь 12, 2023
Abstract
The
employing
visible
light
to
drive
organic
transformations
is
the
most
promising
choice
meet
needs
for
green
synthesis,
in
which
reactions
promoted
by
may
provide
a
more
efficient
and
greener
method.
Currently,
abundant
methods
activation
functionalization
of
reaction
substrates
have
relied
on
direct
single‐electron
transfer
(SET)
between
excited
photocatalyst
substrates,
these
wonderful
works
were
summarized
docoumented
many
reviews.
As
complement
above
reactions,
photoredox‐mediated
atom
(photocatalyst‐to‐HAT
catalyst‐to‐substrates)
generate
radical
species
are
showing
an
explosively
growing
trend.
In
this
review,
we
highlight
recent
significant
developments
rapidly
area,
mainly
focusing
photoinduced
base‐to‐substrates
charge
reactions.
Green Chemistry,
Год журнала:
2024,
Номер
26(17), С. 9371 - 9377
Опубликована: Янв. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(8), С. 1981 - 1987
Опубликована: Янв. 1, 2023
A
photoinduced
radical
[1,2]-Brook
rearrangement/defluorinated
alkylation
reaction
of
α-trifluoromethyl
alkenes
with
α-silyl
alcohols
was
developed
for
facile
access
to
gem
-difluoro
homoallylic
alcohol
derivatives.
Organic Letters,
Год журнала:
2023,
Номер
26(1), С. 100 - 105
Опубликована: Дек. 26, 2023
Herein,
we
report
a
photoredox
enabled
defluorinative
benzylation
of
trifluoromethyl
alkenes
with
readily
available
alkylarenes,
which
provides
convenient
access
to
series
structurally
valuable
benzylated
gem-difluoroalkenes
under
mild
reaction
conditions.
The
synthetic
value
this
protocol
has
been
demonstrated
by
the
transformations
several
substrates
bearing
drug
moieties,
gram-scale
reactions,
and
various
further
derivatizations
gem-difluoroalkene
products.
preliminary
mechanistic
investigations
suggest
pathway
rate-determining
benzyl
C–H
bond
cleavage
toluene
followed
benzylic
radical
formation.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(5), С. 1305 - 1313
Опубликована: Янв. 1, 2024
A
conceptually
novel
single
electron
transfer
strategy
for
C(sp3)–F
activation-enabled
[3
+
2
1]
annulation
of
α-polyfluoromethyl
alkenes
is
developed.
