Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 24, 2024
ConspectusClassical
education
in
organic
chemistry
and
catalysis,
not
the
least
my
own,
has
centered
on
two-electron
transformations,
from
nucleophilic
attack
to
oxidative
addition.
The
focus
is
well-founded,
as
this
brand
of
enabled
incredible
feats
synthesis,
development
life-saving
pharmaceuticals
production
ubiquitous
commodity
chemicals.
With
that
said,
approach
many
ways
complementary
nature,
where
enzymes
frequently
make
use
single-electron
"radical"
steps
achieve
challenging
reactions
with
exceptional
selectivity,
including
light
detection
C-H
hydroxylation.
While
power
radical
elementary
undeniable,
fundamental
understanding
of─and
ability
apply─these
catalysis
remains
underdeveloped,
constraining
palette
which
chemists
can
new
reactions.Motivation
remedy
traditional
underemphasis
been
intensified
by
runaway
success
outer-sphere
photoredox
only
confirming
versatility
radicals
anthropogenic
but
also
teaching
value
robust
well-understood
catalytic
cycles
for
reaction
design.
Indeed,
I
would
argue
fueled
strong
its
underlying
steps,
consideration
transfer
(SET)
energetics
allowing
be
designed
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3081 - 3085
Опубликована: Апрель 3, 2024
γ-Spirolactam
is
a
privileged
building
block
that
found
in
wide
range
of
natural
products
and
bioactive
compounds.
Herein,
we
report
an
arenethiolate-catalyzed
1,5-HAT
aryl
halides
to
obtain
γ-spirolactams
through
SET
reduction/intramolecular
1,5-HAT/cyclization/HAT
process.
This
protocol
features
metal-free
conditions
broad
substrate
scope,
furnishing
the
moderate
excellent
yields.
Notably,
bromides,
chlorides
even
fluorides
are
well
tolerated
this
transformation.
A
mechanism
involving
arenethiolate
as
catalyst
proposed
based
on
DFT
calculation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 23321 - 23329
Опубликована: Авг. 6, 2024
Pyridoxal-5'-phosphate
(PLP)
and
derivatives
of
this
cofactor
enable
a
plethora
reactions
in
both
enzyme-mediated
free-in-solution
transformations.
With
few
exceptions
each
category,
such
chemistry
has
predominantly
involved
two-electron
processes.
This
sometimes
poses
significant
challenge
for
using
PLP
to
build
tetrasubstituted
carbon
centers,
especially
when
the
reaction
is
reversible.
The
ability
access
radical
pathways
paramount
broadening
scope
catalyzed
by
coenzyme.
In
study,
we
demonstrate
PLP-based
intermediate
engage
number
C-C
bond-forming
reactions.
By
selection
an
appropriate
oxidant,
single-electron
oxidation
quinonoid
can
be
achieved,
which
subsequently
applied
Through
pathway,
synthesized
series
α-tertiary
amino
acids
esters
investigate
substrate
identify
nonproductive
pathways.
Beyond
acid
model
system,
that
other
classes
amine
substrates
range
small
molecule
reagents
serve
as
coupling
partners
semiquinone
radical.
We
anticipate
versatile
species
will
central
development
novel
Organic Letters,
Год журнала:
2023,
Номер
25(35), С. 6598 - 6602
Опубликована: Авг. 29, 2023
A
method
for
hydrofluoroalkylation
of
alkenes
with
trifluoroacetic
esters
under
visible
light
irradiation
affording
difluorinated
products
is
described.
The
reaction
involves
readily
available
trimethyltriazinane
as
a
shoichiometric
reducing
agent,
which
generates
diamino-substituted
alkyl
radical
serving
strong
electron
donor.
It
believed
that
the
cleavage
C–F
bond
by
triazinane-derived
single
reduction
coupled
fluoride
transfer.
Tetrahedron Chem,
Год журнала:
2025,
Номер
unknown, С. 100119 - 100119
Опубликована: Янв. 1, 2025
An
efficient
strategy
for
intramolecular
oxidative
cyclization
of
2-alkynylthioanisoles
toward
3-acylbenzo[b]thiophenes
by
photochemical
hydrogen
atom
transfer
catalysis
has
been
developed.
3-Acylbenzo[b]selenophenes,
benzofurans
and
indoles
can
also
be
prepared
this
protocol.
This
reaction
is
convenient
to
perform
at
room
temperature
under
simple
conditions
using
air
as
the
oxidant.
Mechanistic
studies
revealed
that
formation
α-thioalkyl
radicals
intermediate
crucial.Graphical
abstract
European Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Abstract
A
visible‐light‐induced
deuterodichloromethylation
of
alkenes
was
developed
with
readily
available
and
inexpensive
deuterochloroform
as
the
reagent.
Silacarboxylic
acids,
which
could
generate
silyl
radicals
through
efficient
decarboxylation,
were
applied
halogen
atom
transfer
agents.
series
deuterium‐containing
gem
‐dichloroalkanes
prepared
in
good
yields.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 14, 2025
Direct
acylation
of
heteroarenes
with
aldehydes
has
been
established
through
a
photoinduced
hypervalent
iodine-mediated
cross-dehydrogenative
coupling
reaction.
The
reaction
proceeds
the
in
situ
generation
nucleophilic
acyl
radicals
from
via
C-H
hydrogen
atom
transfer
(HAT),
followed
by
Minisci-type
heteroarenes.
developed
system
proved
to
be
suitable
for
cross-coupling
diverse
range
heterocycles
and
aldehydes.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2829 - 2833
Опубликована: Янв. 1, 2024
Commodity
chemicals
are
used
as
alkylating
and
reducing
agents
for
radical
addition
to
alkenes.
The
method
is
based
on
activation
of
the
strong
C–Cl
bond
by
anion
carbon
dioxide.
Chemical Science,
Год журнала:
2024,
Номер
15(25), С. 9612 - 9619
Опубликована: Янв. 1, 2024
Herein,
we
report
a
peptide
cyclisation
strategy
via
intramolecular
interception
of
cysteine
desulfurisation.
This
method
enables
the
unprotected
peptides
in
aqueous
solution
installation
hydrocarbon
linkage.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(17), С. 4757 - 4761
Опубликована: Янв. 1, 2024
A
visible
light-induced
organophotocatalytic
strategy
for
dehalogenative
deuteration
of
a
wide
variety
primary,
secondary,
and
tertiary
alkyl
bromides
is
reported.
