Abstract
The
reactivity
of
the
carbon
dioxide
radical
anion
(CO2•−)
toward
alkenes
has
garnered
remarkable
attention
owing
to
its
potential
synthesize
valuable
organic
compounds.
Herein,
we
report
reactions
between
CO2•−
and
1,6-dienes,
yielding
5-membered
lactam
derivatives
via
highly
trans-selective
5-exo-trig
cyclization.
Both
carboxylative
cyclization
hydrocyclization
occur
with
up
74%
combined
yield.
Computational
studies
show
that
transition
state
during
favors
trans-configuration
over
cis-configuration.
This
work
offers
new
insights
into
synthesis
N-heterocycles.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 6178 - 6183
Опубликована: Янв. 1, 2024
Low-cost
formate
salt
was
used
as
the
reductant
and
part
of
carboxyl
source
in
a
visible-light-driven
dicarboxylation
diverse
alkenes,
including
simple
styrenes.
The
highly
competing
hydrocarboxylation
side
reaction
successfully
overridden.
Good
yields
products
were
obtained
under
mild
conditions
at
ambient
temperature
pressure
CO
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16982 - 16989
Опубликована: Июнь 13, 2024
Catalytic
asymmetric
dearomatization
(CADA)
reactions
have
evolved
into
an
efficient
strategy
for
accessing
chiral
polycyclic
and
spirocyclic
scaffolds
from
readily
available
planar
aromatics.
Despite
the
significant
developments,
CADA
reaction
of
naphthalenes
remains
underdeveloped.
Herein,
we
report
a
Gd(III)-catalyzed
naphthalene
with
PyBox
ligand
via
visible-light-enabled
[4
+
2]
cycloaddition.
This
features
application
Gd/PyBox
complex,
which
regulates
reactivity
selectivity
simultaneously,
in
excited-state
catalysis.
A
wide
range
functional
groups
is
compatible
this
protocol,
giving
highly
enantioenriched
bridged
polycycles
excellent
yields
(up
to
96%)
>20:1
chemoselectivity,
dr,
>99%
ee).
The
synthetic
utility
demonstrated
by
2
mmol
scale
reaction,
removal
directing
group,
diversifications
products.
Preliminary
mechanistic
experiments
are
performed
elucidate
mechanism.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9283 - 9293
Опубликована: Июнь 4, 2024
The
direct
reductive
functionalization
of
alkynes
under
mild
conditions
presents
a
promising
yet
challenging
avenue
for
accessing
value-added
molecules.
Alkyne
radical
anions
represent
distinct
class
reactive
intermediates
characterized
by
both
charge
and
an
unpaired
electron,
thus
holding
great
potential
facilitating
diverse
bond
formations,
particularly
in
alkyne
functionalization.
However,
the
synthetic
utility
is
limited,
primarily
due
to
difficulty
their
generation
formation
highly
unstable
vinyl
intermediates.
In
this
study,
we
accomplished
from
aryl
feedstocks
via
single
electron
transfer
(SET)
reduction
with
photogenerated
CO2
anion
(CO2•–),
enabling
hydroalkylation,
arylalkenylation,
hydrocarboxylation
alkynes.
Our
photocatalytic
strategy
features
metal-free
catalysis,
reaction
conditions,
employment
traceless
reductant,
good
functional
group
compatibility,
step-
atom-economy,
high
regioselectivity.
This
study
not
only
paves
way
leveraging
underexplored
but
also
catalyzes
ongoing
exploration
bifunctional
CO2•–
species
chemistry.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 11967 - 11973
Опубликована: Июль 26, 2024
Herein,
a
photoredox-neutral
strategy
for
carboxylation
of
acylated
alcohols
via
C(sp3)–O
bond
activation
and
cleavage
with
tetrabutylammonium
oxalate
(TBAO)
as
the
carbonyl
source
reductant
well
promoter
is
described.
Neither
pre-established
CO2
atmosphere
nor
external
electron
donors
are
required
TBAO
crucial
transformation.
Various
primary,
secondary,
tertiary
could
be
smoothly
converted
to
corresponding
aryl
acetic
acids,
which
core
structures
diverse
pharmaceutical
drugs.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(21), С. 4274 - 4293
Опубликована: Авг. 17, 2024
Abstract
Formates
are
abundantly
available
and
inexpensive
commodity
chemical,
widely
used
in
laboratory
industrial
organic
synthesis.
promising
hydrogen
carrier
green
C1
source,
have
also
been
a
subject
of
research
as
SET
reductants
recent
years.
Compared
to
the
toxic
flammable
gas
carbon
monoxide,
which
serves
formates
easier
handle,
store,
transport,
more
environmentally
friendly.
Therefore,
studies
radical
reactions,
formate
is
not
only
an
ideal
source
carbonyl,
great
significance
synthesize
carboxyl
compounds
with
various
structures,
but
reductant
for
editing
molecules
either
scientific
or
production.
The
activation
conversion
formate,
reductant,
very
challenging
hot
field
Chemical Science,
Год журнала:
2024,
Номер
15(9), С. 3165 - 3173
Опубликована: Янв. 1, 2024
NHC–CO
2
–borane
compounds
were
shown
to
be
reduced
by
one
electron
at
a
reduction
potential
as
mild
−1.34
V
vs.
Fc
+/0
.
The
resulting
radical
anion
was
crystallographically
characterised
and
showed
reactivity
similar
that
of
the
CO
anion.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 18, 2025
Comprehensive
Summary
We
have
developed
a
series
of
1‐methylpyridine‐2(1
H
)‐thione
(MPT)
analogues
to
be
used
as
organocatalysts.
The
MPT
catalysts
are
easily
prepared
and
bench‐stable.
In
our
previous
work,
we
found
that
the
ground‐state
catalyst
could
act
nucleophile
generate
primary
radicals
via
an
S
N
2
pathway.
However,
this
reaction
was
limited
benzyl
radicals.
Herein,
reported
new
catalytic
property
catalyst.
photoexcited
(
E
(MPT
·+
/MPT*)
=
–1.60
V
vs.
Ag/AgCl
in
MeCN)
reduce
NHPI
esters
through
single
electron
transfer
process.
Various
carbon
radicals,
including
radical,
well
primary,
secondary
tertiary
alkyl
generated
easily.
Notably,
amino
acids,
peptide,
pharmaceuticals,
other
biologically
active
molecules
modified
by
using
methodology
showing
potential
synthetic
utility
method.
