Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(47), P. 10096 - 10101
Published: Nov. 15, 2024
A
photoredox
C(sp3)–H
alkenylation–dehydrogenation
of
o-iodoarylalkanols
with
terminal
alkynes
for
the
synthesis
(E)-
and
(Z)-quaternary
carbon
center-containing
pent-4-en-1-ones
is
described.
The
stereoselectivity
depends
on
utilization
photocatalysts.
While
using
an
organic
photocatalyst
like
4-DPAIPN
manipulates
arylalkynes
to
assemble
(E)-pent-4-en-1-ones,
in
case
Ir
potocatalyst
such
as
Ir(ppy)2(dtbbpy)PF6
reaction
delivers
(Z)-pent-4-en-1-ones.
For
alkylalkynes,
furnishes
(E)-pent-4-en-1-ones
exclusively
presence
or
Ir(ppy)2(dtbbpy)PF6.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 7922 - 7930
Published: March 18, 2024
Chromoselective
bond
activation
has
been
achieved
in
organic
helicenium
(nPr-DMQA+)-based
photoredox
catalysis.
Consequently,
control
over
chromoselective
C(sp2)–X
multihalogenated
aromatics
demonstrated.
nPr-DMQA+
can
only
initiate
the
halogen
atom
transfer
(XAT)
pathway
under
red
light
irradiation
to
activate
low-energy-accessible
C(sp2)–I
bonds.
In
contrast,
blue
initiates
consecutive
photoinduced
electron
(conPET)
more
challenging
C(sp2)–Br
Comparative
reaction
outcomes
have
demonstrated
α-arylation
of
cyclic
ketones
with
and
lights.
Furthermore,
red-light-mediated
selective
bonds
activated
iodobromoarenes
keep
bromo
functional
handle
untouched.
Finally,
strength
catalysis
highlighted
two-fold
functionalization
using
both
photo-to-transition
metal
photo-to-photocatalyzed
transformations.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2440 - 2444
Published: March 19, 2024
An
iodoarene-driven
electroreductive
remote
C(sp3)–H
arylation
of
unsymmetrical
1-(o-iodoaryl)alkyl
ethers
with
cyanoarenes
for
the
site
selective
synthesis
α-(hetero)aryl
is
developed.
With
introduction
as
both
aryl
sources
and
electron
transfer
mediators,
this
method
includes
an
strategy
to
enable
regiocontrollable
formation
two
new
bonds,
one
C(sp2)–H
bond,
C(sp2)–C(sp3)
in
a
single
reaction
step
through
sequence
halogen
atom
(XAT),
hydrogen
(HAT),
radical–radical
coupling,
decyanation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(28)
Published: April 15, 2024
With
halogen-atom
transfer
as
an
effective
tool,
a
novel
catalytic
enantioselective
protocol
to
generate
chiral
trifluoromethylated
alkynes
has
been
established
by
cooperative
photoredox
and
nickel
catalysis
system,
providing
straightforward
modular
route
access
this
type
of
product
in
good
yields
enantioselectivities.
The
process
is
essential
for
the
reaction
strategy
offers
another
promising
way
utilize
alkyl
halides
with
highly
negative
reduction
potentials.
It
firstly
expands
nickel-catalyzed
asymmetric
reductive
cross-couplings
organohalides
from
traditional
single-electron
transfer.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 1294 - 1304
Published: Jan. 7, 2025
Given
the
widespread
presence
of
spirocyclic
scaffolds
in
natural
products
and
pharmacologically
relevant
synthetic
compounds,
development
efficient
methodologies
for
their
construction
holds
great
importance
medicinal
chemistry
pharmaceutical
research.
In
this
study,
a
general
photochemical
dearomative
spirocyclization
nonactivated
arenes
has
been
established.
The
key
to
method
lies
ability
amine-borane
radicals
activate
aryl
bromides
iodides
via
halogen-atom
transfer,
thereby
allowing
conversion
halides
into
corresponding
subsequent
chemodivergent
transformations.
remarkable
compatibility
versatility
1,4-difunctionalization
is
showed
by
rapid
assembly
structurally
diverse
1,4-cyclohexadiene-based
spirocycles
incorporating
oxindole,
indoline,
or
dihydrobenzofuran
subunits.
Moreover,
potential
utility
protocol
exemplified
formal
total
synthesis
vasopressin
V2
receptor
antagonist
Satavaptan.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 20, 2025
We
report
the
enantioselective
hydrodifluoroalkylation
of
alkenes
proceeding
via
an
asymmetric
hydrogen
atom
transfer
(HAT)
event
catalyzed
by
thiol-containing
tetrapeptides.
Photocatalytic
generation
a
difluoroacetyl
radical
followed
carbon–carbon
bond
formation
results
in
prochiral
carbon-centered
that
engages
with
chiral
catalyst.
A
trialkylamine
reductant
is
proposed
to
turn
over
catalyst
this
net-reductive
transformation.
Notably,
incorporating
(S)-β-methyl-substituted
cysteine
as
N-terminal
residue
improved
selectivity
relative
native
(Cys)
residue,
and
X-ray
crystallographic
analysis
supports
conformational
underpinning
effect.
range
enantioenriched
γ-substituted
amides
were
synthesized
up
96:4
enantiomeric
ratio,
demonstrating
broad
functional
group
tolerance
method.
Models
accounting
for
induction
are
supporting
DFT
calculations.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(30), P. 12077 - 12085
Published: Jan. 1, 2024
Electron
transfer
to
the
2
LMCT
state
of
a
photoactive
complex
based
on
Earth-abundant
iron
has
been
used
drive
photocatalytic
aminomethylation
reactions
by
generation
α-aminoalkyl
radicals
and
underlying
mechanism
investigated.
