Metallaphotoredox
cross-coupling
is
a
well-established
strategy
for
generating
clinically
privileged
aliphatic
scaffolds
via
open-shell
reactivity.
The
introduction
of
new
C(sp3)-coupling
partners
within
this
paradigm
can
provide
entry
to
novel,
medicinally-relevant
chemical
space.
Alkenes
are
abundant,
bench-stable
and
undergo
facile
C(sp3)-radical
reactivity
metal-hydride
hydrogen
atom
transfer
(MHAT),
yet
metallaphotoredox
methodologies
invoking
remain
underdeveloped.
Importantly,
the
merger
MHAT
activation
with
catalysis
could
enable
olefins
feedstock
radical
only
activated
photocatalysis,
such
as
alcohols.
Herein,
we
report
first
C(sp3)–C(sp3)
coupling
MHAT-activated
alkenes
alcohols
(i.e.
deoxygenative
hy-droalkylation)
triple
co-catalysis.
Through
synergistic
Ir
Mn
Ni
sorting
pathways,
branch-selective
protocol
pairs
diverse
methanol
or
primary
alcohols,
displays
remarkable
functional
group
tolerance,
enables
rapid
construction
complex
frameworks.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1110 - 1115
Опубликована: Янв. 26, 2024
Despite
the
significant
success
of
decarboxylative
radical
reactions,
catalytic
systems
vary
considerably
upon
different
acceptors,
requiring
renewed
case-by-case
reaction
optimization.
Herein,
we
developed
an
iron
condition
that
enables
highly
efficient
decarboxylation
various
carboxylic
acids
for
a
range
transformations.
This
operationally
simple
protocol
was
amenable
to
wide
array
delivering
structurally
diverse
oxime
ethers,
alkenylation,
alkynylation,
thiolation,
and
amidation
products
in
useful
excellent
yields
(>40
examples,
up
95%
yield).
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2381 - 2386
Опубликована: Март 15, 2024
Organic
sulfones
are
an
important
class
of
chemical
compounds
widely
used
in
many
research
fields.
The
direct
decarboxylative
sulfonylation
carboxylic
acids
is
attractive
but
challenging,
particularly
when
iron
as
a
metal
catalyst.
Herein,
we
describe
photoinduced
iron-catalytic
method
for
the
synthesis
directly
using
via
radical-based
decarboxylation.
This
protocol
mild,
highly
efficient,
and
easy-to-operate.
A
broad
scope
carbon
electrophiles
could
be
well
tolerated.
mechanism
involving
iron-catalyzed
decarboxylation,
radical
transfer,
single-electron
reduction,
nucleophilic
attack
proposed.
Organic Letters,
Год журнала:
2024,
Номер
26(3), С. 713 - 718
Опубликована: Янв. 12, 2024
Sulfonamides
are
important
structures
in
pharmaceuticals,
agrochemicals,
and
organocatalysts,
yet
the
rapid
benign
synthesis
of
these
compounds
is
still
a
great
challenge.
Herein
we
report
photoinduced
method
for
synthesizing
sulfonamides
from
(hetero)aryl
carboxylic
acid
oxime
esters.
This
reaction
proceeds
via
one-pot
cascade
radical–radical
cross-coupling
by
energy-transfer-mediated
photocatalysis.
A
wide
substrate
scope
including
substrates
late-stage
modification
pharmaceutical
molecular
entities
reveal
its
generality.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5227 - 5235
Опубликована: Март 21, 2024
Sulfonamides
are
prominently
featured
in
organic
synthesis
and
medicinal
chemistry.
Yet,
a
general
synthetic
platform
for
the
modular
construction
of
aryl
sulfonamides
remains
elusive.
Herein,
metal-free
photoredox-catalyzed
three-component
via
an
sulfonyl
ammonium
salt
intermediate,
which
was
generated
situ
SET
event,
has
been
established.
A
variety
structurally
diverse
primary,
secondary,
tertiary
were
synthesized
rapidly
from
abundant
amines
or
sodium
azide
under
mild
conditions.
Notably,
primary
aliphatic
amine,
challenging
Cu-catalyzed
protocols,
worked
well
this
approach.
Moreover,
fluoride
can
be
accessed
smoothly
as
well,
using
potassium
hydrogen
nucleophile.
The
potential
utility
conversion
is
demonstrated
facile
three
bioactive
drug
compounds.
Preliminary
mechanistic
studies
have
revealed
that
radical
key
intermediates
mechanistically
innovative
methodology.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(3), С. 1898 - 1909
Опубликована: Янв. 19, 2024
A
method
to
assemble
(hetero)aryl
sulfonamides
via
the
reductive
coupling
of
aryl
sulfinates
and
nitroarenes
is
reported.
Various
reducing
conditions
with
sodium
bisulfite
or
without
tin(II)
chloride
in
DMSO
were
developed
using
an
ultrasound
bath
improve
reaction
homogeneity
mixing.
range
bearing
a
selection
functional
groups
prepared,
mechanism
transformation
was
investigated.
These
investigations
have
led
us
propose
formation
nitrosoarene
intermediates,
which
established
independent
molecular
strategy.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13536 - 13545
Опубликована: Май 2, 2024
Herein,
we
establish
a
remote
hydrosulfonamidation
(HSA)
of
alkenes
using
palladium
catalysis,
where
N-fluoro-N-(fluoro-sulfonyl)-carbamate
with
sulfur(VI)
fluoride
moiety
is
demonstrated
as
good
amidation
reagent.
The
anti-Markovnikov
HSA
reaction
terminal
and
the
internal
are
achieved
to
efficiently
yield
primary
N-alkyl-N-(fluorosulfonyl)-carbamates.
In
addition,
this
protocol
enables
high-value
utilization
alkane
by
combining
dehydrogenation
process.
generated
N-alkyl
products
exhibit
unique
reactivity
fluorides,
which
can
be
directly
transferred
sulfamides
or
amines
via
exchange
reaction,
thereby
streamlining
their
synthesis.
Moreover,
(pyridyl)
benzazole-type
ligand
proved
vital
for
excellent
chemo-
regioselectivities.
Chemical Communications,
Год журнала:
2024,
Номер
60(72), С. 9645 - 9658
Опубликована: Янв. 1, 2024
This
highlight
article
summarizes
the
complete
development
of
photodecarboxylative
functionalization
free
carboxylic
acids
via
a
concerted
single
electron
transfer
(SET)
or
energy
(ET)
pathways.
