ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 15991 - 16011
Опубликована: Ноя. 28, 2023
Carbon
dioxide
radical
anion
(CO2•–)
is
a
highly
reactive
nucleophilic
species
that
has
recently
emerged
in
organic
chemistry
as
strong
single
electron
donor
(reductant)
and
reactant
for
the
synthesis
of
carboxylic
acids.
In
general,
CO2•–
can
be
generated
by
either
direct
reduction
CO2
or
HAT
formate
salts.
Achievements
reactions
involving
have
been
witnessed
recent
years.
This
Review
summarizes
advances
highlighting
some
challenges
identifying
potential
areas
improvement,
which
may
offer
inspiration
future
studies.
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 883 - 888
Опубликована: Янв. 22, 2024
Herein,
we
present
a
transition-metal-free,
easy
handling
protocol
for
regioselective
carboxylation
of
gem-difluorostyrenes
with
sodium
formate
as
the
C1
source.
30
examples
α-fluoracrylates
were
obtained
in
yields
to
80%
under
these
conditions.
A
defluorinative
monofluorovinyl
intermediate
and
consecutive
photoinduced
electron
transfer
mechanism
proposed
after
investigation.
Molecules,
Год журнала:
2023,
Номер
28(16), С. 6127 - 6127
Опубликована: Авг. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(4)
Опубликована: Окт. 9, 2023
The
advancement
of
sustainable
photoredox
catalysis
in
synthetic
organic
chemistry
has
evolved
immensely
because
the
development
versatile
and
cost-effective
reagents.
In
recent
years,
a
substantial
effort
been
dedicated
to
exploring
utility
formic
acid
salts
various
photochemical
reactions.
this
context,
formates
have
demonstrated
diverse
capabilities,
functioning
as
reductants,
sources
carbonyl
groups,
reagents
for
hydrogen
atom
transfer.
Notably,
CO
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16760 - 16770
Опубликована: Июль 24, 2023
The
need
for
carbon-labeled
radiotracers
is
increasingly
higher
in
drug
discovery
and
development
(carbon-14,
β-,
t1/2
=
5730
years)
as
well
positron
emission
tomography
(PET)
vivo
molecular
imaging
applications
(carbon-11,
β+,
20.4
min).
However,
the
structural
diversity
of
still
systematically
driven
by
narrow
available
labeled
sources
methodologies.
In
this
context,
emergence
carbon
dioxide
radical
anion
chemistry
might
set
forth
potential
unexplored
opportunities.
Based
on
a
dynamic
isotopic
equilibration
between
formate
salts
[13C,
14C,
11C]CO2,
C-labeled
CO2•-
could
be
accessed
under
extremely
mild
conditions
within
seconds.
This
methodology
was
successfully
applied
to
hydrocarboxylation
dicarboxylation
reactions
late-stage
isotope
labeling
pharmaceutically
relevant
compounds.
relevance
method
radiochemistry
showcased
whole-body
PET
biodistribution
profile
[11C]oxaprozin
mice.
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
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(2), С. 1262 - 1268
Опубликована: Янв. 5, 2024
A
concise
enantioselective
total
synthesis
of
(−)-daphenylline,
a
hexacyclic
Daphniphyllum
alkaloid
with
unique
benzene
ring,
was
achieved
in
14
steps.
The
commences
two
chiral
stereocenters,
C2
and
C18,
readily
installed
via
Carreira's
Ir/amine
dual-catalyzed
allylation.
allylic
bridgehead
amine
6
rapidly
prepared
through
Wickens'
photoredox-catalyzed
hydrocarboxylation
olefin
CuBr2-catalyzed
α-amination
ketone.
tetracycle
4
formed
Pd-catalyzed
reductive
Heck
reaction
or,
more
concisely,
by
Krische's
Rh-catalyzed
1,6-enyne
cyclization.
In
this
synthesis,
newly
reported
used
twice,
Friedel–Crafts
acylation
thrice.
