ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8270 - 8293
Опубликована: Май 13, 2024
As
one
of
the
most
important
key
intermediates,
NHC-bound
acylazolium-based
ionic
transformations
have
been
intensively
explored
in
past
two
decades.
With
expeditious
development
NHC-catalyzed
radical
recent
years,
acylazolium
chemistry
has
reached
another
level,
with
number
relevant
publications
increasing
significantly.
However,
a
summary
focused
on
acylations
NHC-derived
acyl
azoliums
classified
according
to
mechanistic
difference
not
reported.
Such
detailed
classification
and
deep
analysis
provide
opportunities
for
better
understanding
history
trend
this
field.
In
review,
reactions
N-heterocyclic
carbene
(NHC)-derived
are
systematically
introduced.
The
achievements
challenges
within
area
also
summarized
discussed
at
end.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(18), С. 4488 - 4515
Опубликована: Янв. 1, 2023
This
review
highlights
the
recent
advances
in
radical
acylated
difunctionalization
of
unsaturated
carbon–carbon
bonds
and
focuses
on
mechanistic
insights
these
transformations.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6451 - 6461
Опубликована: Апрель 12, 2024
Given
the
abundance
of
alcohol
feedstocks
and
significance
disulfides,
we
herein
report
a
nickel-catalyzed
direct
deoxygenative
disulfuration
alcohols
with
trisulfide
dioxides
to
access
wide
range
disulfide
molecules
without
cumbersome
decoration
coupling
partners.
The
use
readily
available
dicyclohexylcarbodiimide
form
transient
isoureas
provides
activation
high
bond
dissociation
energy
C–O
bond,
which
facilitates
straightforward
conversion
nonderivatized
forge
C–SS
bond.
Notably,
this
method
obviates
preactivation
multistep
procedure
catalytic
turnover
under
exogenous
ligand
base-free
conditions,
featuring
broad
substrate
scope
functional
group
compatibility.
It
thus
offers
robust
alternative
existing
methods
for
precise
construction
versatile
compounds
from
more
abundant
commercially
substrates.
synthetic
utility
was
further
showcased
by
successful
gram-scale
experiments
structurally
complex
pharmaceuticals.
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13451 - 13496
Опубликована: Авг. 26, 2024
Alcohols
are
abundant
with
versatile
structural
variety
and
have
ample
use
as
pivotal
functional
groups
in
numerous
organic
processes.
Because
of
their
frequent
occurrence
enumerable
natural
products,
bioactive
molecules,
medicinal
components,
alcohol
functionalities
provide
a
promising
scope
research
to
advance
the
operational
diversity
for
improving
clinical
success.
Recent
years
witnessed
design
modern
C–C
C–heteroatom
bond-forming
approaches
easily
accessible
commercially
available
unactivated
aliphatic
alcohols
native
adaptive
sp3
handles,
hence
offering
groundbreaking
transformative
pathways
functionalization
complex
molecular
architectures.
The
judicial
application
appropriate
activating
generate
alkyl
radical
from
through
C–O
bond
fragmentation
employ
it
potential
alkylating
agent
unfolds
unique
synthetic
strategies,
thereby
replacing
obvious
requirement
halides.
This
review
elaborately
discusses
recent
trends
regarding
using
C(sp3)-centered
various
chemical
transformations
by
exploiting
different
activation
modes
disrupter
under
photoredox
catalysis.
presentation
is
organized
nature
scaffolds,
kind
formation,
progress
achieved
this
domain
since
original
discovery
providing
illustrative
examples
mechanistic
details,
focus
on
difficulties
future
prospects.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
unknown
Опубликована: Окт. 31, 2023
β-Amino
acids
are
useful
building
blocks
of
bioactive
molecules,
including
peptidomimetics
and
pharmaceutical
compounds.
The
current
limited
accessibility
to
β2,2-type
amino
which
bear
an
α-quaternary
center
has
their
use
in
chemical
synthesis
biological
investigations.
Disclosed
herein
is
the
development
a
new
N-heterocyclic
carbene/photocatalyzed
aminocarboxylation
olefins,
affording
β2,2-amino
esters
with
high
regioselectivity.
generation
nitrogen-centered
radicals
derived
from
simple
imides
via
sequence
deprotonation
single-electron
oxidation
allows
for
subsequent
addition
geminal-disubstituted
olefins
regioselectively.
intermediate
tertiary
then
cross-couple
stabilized
azolium-based
radical
generated
situ
efficiently
construct
quaternary
centers.
Mechanistic
studies,
Stern–Volmer
fluorescence
quenching
experiments,
support
proposed
catalytic
cycle.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(48)
Опубликована: Окт. 11, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
catalyzed
radical‐radical
reactions
have
been
proven
to
be
powerful
strategies
for
assembling
ketyl‐containing
compounds
via
single
electron
transfer
(SET)
pathway
under
either
thermal
conditions
or
photoredox
conditions.
In
this
context,
acylation
of
alkenes
radical
relay
NHC‐organocatalysis
has
also
opened
a
new
window
the
difunctionalization
construct
valuable
molecules
in
organic
synthesis.
review,
advances
and
progress
were
summarized
according
different
ways
generation
key
NHC‐bound
ketyl‐type
radicals.
Furthermore,
reaction
scopes,
limitations
mechanisms
discussed
based
on
types
catalytic
systems.
Conclusions
perspectives
put
forward
at
end.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 6334 - 6344
Опубликована: Апрель 15, 2024
A
one-pot
strategy
for
deoxygenative
alkylation
of
alcohols
with
quinoxalin-2(1H)-ones
was
developed
by
using
xanthate
salts
as
alcohol-activating
groups
radical
generation
in
the
presence
tricyclohexylphosphine
under
visible-light-promoted
conditions.
The
remarkable
features
this
reaction
include
a
broad
substrate
scope,
excellent
functional
group
tolerance,
mild
conditions,
and
simple
operation.
Moreover,
synthetic
utility
validated
success
two-step
reactions,
scale-up
synthesis,
chemoselective
monodeoxygenation
diols.
Organic Letters,
Год журнала:
2024,
Номер
26(11), С. 2197 - 2201
Опубликована: Март 7, 2024
In
this
study,
we
present
an
N-heterocyclic
carbene-catalyzed
method
for
the
radical
acylphosphorylation
of
alkenes.
Electrochemical
investigations
were
employed
to
identify
appropriate
class
oxime
phosphonates
capable
undergoing
a
single-electron
transfer
(SET)
with
Breslow
enolates.
The
resulting
phosphoryl
radicals
effectively
coupled
diverse
styrenes
and
aldehydes
yield
variety
γ-oxo-phosphonates.
Both
clock
experiments
electrochemical
studies
support
our
reaction
design,
plausible
mechanism
organocatalytic
transformation
is
proposed.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3089 - 3099
Опубликована: Янв. 1, 2024
NHC
and
photocatalysis
dual-catalyzed
mono/difluoromethylative
acylation
of
1,3-enynes
was
realized,
providing
fluormethyl-substituted
allenyl
ketones.
SO
2
might
play
a
critical
role
in
achieving
high
reactivity
selectivity.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 16, 2024
The
carboamination
of
unsaturated
molecules
using
bifunctional
reagents
is
considered
an
attractive
approach
for
the
synthesis
nitrogen-containing
compounds.
However,
C-N
have
never
been
employed
in
cyclopropane.
In
this
study,
we
use
N-heterocyclic
carbene
(NHC),
N-benzoyl
saccharin,
as
a
reagent
and
photoredox
catalyst
dual-catalyzed
1,3-aminoacylation
NHCs
play
multiple
roles,
functioning
Lewis
base
catalysts
to
activate
bonds,
promoting
oxidative
quenching
process
PC*,
acting
efficient
acyl
radical
transfer
formation
C-C
bonds.
between
excited-state
PC*
NHC
adduct
key
photooxidation
generality
aryl
cyclopropanes.
