JACS Au,
Год журнала:
2024,
Номер
4(11), С. 4223 - 4233
Опубликована: Ноя. 6, 2024
The
incorporation
of
aromatic
difluoromethyl
motifs
has
proven
to
be
a
fruitful
strategy
for
enhancing
the
therapeutic
profiles
modern
pharmaceutical
candidates.
While
defluorofunctionalization
trifluoromethylarenes
offers
promising
pathway
toward
diverse
compounds,
current
methods
are
predominantly
limited
two-component
reactions.
Multicomponent
cascade
reactions
(MCRs)
involving
transient
radical
still
uncommon
and
highly
sought
after,
owing
their
capacity
rapidly
generate
challenging
molecular
structures.
In
this
study,
we
present
photocatalytic
manifold
that
combines
commercially
available
trifluoromethylarenes,
feedstock
dienes,
various
nucleophiles
achieve
modular
defluorinative
MCR.
This
method
features
mild
reaction
conditions
broad
substrate
scope
with
excellent
functional
group
compatibility.
Furthermore,
protocol
enables
previously
unreported
process
editing
resulting
MCR
adducts.
Preliminary
mechanistic
studies
support
proposed
photoexcited
palladium
catalytic
cycle.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18218 - 18223
Опубликована: Июнь 26, 2024
Branched
allylic
esters
and
carboxylates
are
fundamental
motifs
prevalent
in
natural
products
drug
molecules.
The
direct
C-H
oxygenation
of
internal
alkenes
represents
one
the
most
straightforward
approaches,
bypassing
requirement
for
an
leaving
group
as
classical
Tsuji-Trost
reaction.
However,
current
methods
suffer
from
limited
scope─often
accompanied
by
selectivity
issues─thus
hampering
further
development.
Herein
we
report
a
photocatalytic
platform
general
solution
to
these
problems,
enabling
coupling
diverse
with
carboxylic
acids,
alcohols,
other
Chemical Communications,
Год журнала:
2024,
Номер
60(50), С. 6340 - 6361
Опубликована: Янв. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
ACS Central Science,
Год журнала:
2024,
Номер
10(6), С. 1191 - 1200
Опубликована: Май 15, 2024
1,4-cis-Disubstituted
cyclic
compounds
play
a
pivotal
role
in
pharmaceutical
development,
offering
enhanced
potency
and
bioavailability.
However,
their
stereoselective
modular
synthesis
remains
long-standing
challenge.
Here,
we
report
an
innovative
strategy
for
accessing
these
structures
via
mild
conditions
employing
1,3-dienes/alkyl(aryl)halides
amines.
This
procedure
exhibits
wide
substrate
scope
that
tolerates
various
functional
groups.
The
utility
of
this
method
is
demonstrated
the
efficient
TRPV6
inhibitor,
CFTR
modulator,
other
bioactive
molecules.
Combined
experimental
computational
studies
suggest
hybrid
palladium-catalyzed
radical-polar
crossover
mechanism
crucial
achieving
exceptional
1,4-syn-addition
selectivity
(dr
>
20:1).
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 26, 2025
ConspectusThe
past
decade
has
witnessed
significant
advancements
of
visible-light-induced
photocatalysis,
establishing
it
as
a
powerful
and
versatile
tool
in
organic
synthesis.
The
major
focus
this
field
centered
on
the
development
methodologies
that
either
rely
solely
photocatalysts
or
combine
photocatalysis
with
other
catalytic
methods,
such
transition
metal
catalysis,
to
address
broader
more
diverse
array
transformations.
Within
rapidly
evolving
area,
subfield
we
refer
garnered
attention
due
its
growing
impact
mechanistic
uniqueness.
A
distinguishing
feature
is
dual
functionality
single
complex,
which
not
only
acts
photocatalyst
initiate
photochemical
processes
but
also
functions
traditional
catalyst,
facilitating
key
bond-breaking
bond-forming
events.
As
such,
an
exogenous
required
photocatalysis.
However,
implications
harnessing
both
excited-
ground-state
reactivities
complex
can
extend
beyond
simplification.
One
most
compelling
aspects
area
photoexcited
complexes
exhibit
unique
inaccessible
through
conventional
thermal
photocatalytic
approaches.
These
distinct
be
leveraged
accomplish
novel
transformations
by
engaging
entirely
different
substrate
pool
unlocking
new
known
substrates.In
2016,
our
group
pioneered
use
phosphine-ligated
palladium
catalysts
upon
visible-light
irradiation
engage
substrates
radical
reactions.
In
initial
discovery,
showed
photoexcitation
redirect
well-established
oxidative
addition
Pd(0)
into
aryl
iodides
toward
unprecedented
process,
generating
hybrid
Pd(I)
species.
We
subsequently
extended
strategy
formation
alkyl
radicals
from
halides.
reactive
intermediates
have
been
harnessed
wide
variety
transformations,
including
desaturation,
Heck
reactions,
alkene
difunctionalization
cascades,
among
others.Seeking
further
expand
avenue,
achieved
first
example
asymmetric
context
allylic
C–H
amination,
where
catalyst
now
plays
triple
duty
additionally
controlling
stereochemical
outcome
reaction.
parallel
reaction
established
diazo
compounds,
strained
molecules,
electron-deficient
alkenes
serve
precursors
halides
redox-active
esters.
Notably,
engagement
made
possible
photoinduced
hydricity
enhancement
Pd–H
species,
representing
mode
reactivity.This
Account
presents
discovery
organized
type
explored.
Given
rapid
progress
field,
anticipate
will
provide
readers
guiding
principles
inspiration
for
designing
developing
efficient
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21231 - 21238
Опубликована: Июль 29, 2024
Asymmetric
Pd-catalyzed
three-component
carboamination
reactions
of
dienes
to
construct
chiral
cyclohexenylamines,
which
are
great
importance
in
many
fields
chemistry,
have
remained
largely
unexplored.
Here,
we
demonstrate
a
highly
enantio-
and
regioselective
Pd/Ming-Phos-catalyzed
1,3-cyclohexadiene
with
readily
available
aryl
iodides
anilines
for
facile
access
diverse
valuable
cyclohexenylamines.
The
process
shows
excellent
functional
group
tolerance,
easy
scalability,
mild
conditions.
Moreover,
mechanistic
studies
suggest
that
this
reaction
has
first-order
dependence
on
the
concentration
palladium
catalyst
aniline.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(28)
Опубликована: Май 20, 2024
Abstract
In
recent
years,
the
functionalization
of
1,3‐butadiene
has
become
an
attractive
strategy
for
constructing
allyl
compounds
with
molecular
and
structural
complexity,
current
research
focuses
on
synthetic
chemistry
organic
synthesis.
Compared
traditional
synthesis
method,
methods
promoted
by
photochemistry
or
electrochemistry
represent
environmentally
friendly
mild
strategy.
this
review,
reactions
under
photochemical/electrochemical
processes
in
years
are
reviewed
according
to
classification
systems,
particular
emphasis
corresponding
reaction
mechanism,
which
lays
a
foundation
further
exploration
new
catalytic
methods.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Сен. 17, 2024
Allylic
sulfones
are
valuable
motifs
due
to
their
medicinal
and
biological
significance
versatile
chemical
reactivities.
While
direct
allylic
C-H
sulfonylation
represents
a
straightforward
desirable
approach,
these
methods
primarily
restricted
terminal
alkenes,
leaving
the
engagement
of
internal
counterparts
formidable
challenge.
Herein
we
report
photocatalytic
approach
that
accommodates
both
cyclic
acyclic
alkenes
with
diverse
substitution
patterns
electronic
properties.
Importantly,
obtained
can
be
readily
diversified
into
wide
range
products,
thus
enabling
formal
alkene
transposition
all-carbon
quaternary
center
formation
through
sequential
functionalization.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
discusses
emerging
strategies
in
three-component,
stereoselective
C–N
bond-forming
alkene
difunctionalization,
emphasizing
mechanistic
innovations
and
their
impact
on
synthetic
organic
chemistry.
