Abstract
A
computational
study
on
the
reaction
mechanism
of
effective
synthesis
sulfonated
benzo[
b
]oxepinones
and
chromanes
by
radical
cascade
cyclization
is
carried
out
employing
density
functional
theory
(DFT).
Based
our
computations,
rate‐determining
step
formation
arylsulfonyl
for
scheme.
Our
calculations
show
that
1,8‐
1,7‐enynes
with
proceeds
forming
more
thermodynamically
stable
intermediates.
Therefore,
1,8‐enynes
prefer
7‐
exo
‐trig
cyclization,
while
6‐
cyclization.
computations
are
consistent
experimental
results
1,7‐enynes.
Moreover,
if
in
a
proton‐free
solvent,
elimination
product
can
be
obtained
from
1,7‐enyne.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(23), С. 16556 - 16565
Опубликована: Ноя. 16, 2023
Herein,
an
N-heterocyclic
carbene
(NHC)-catalyzed
tandem
cyclization/addition/cyclization
reaction
of
2-isocyanobiaryls
and
α-bromo-N-cinnamylamides
for
the
synthesis
2-pyrrolidinone-functionalized
phenanthridines
is
developed.
This
protocol
features
a
radical
cascade
process,
broad
substrate
scope,
good
functional
group
compatibility
under
metal-
oxidant-free
conditions.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3524 - 3541
Опубликована: Июль 3, 2024
Abstract
The
radical
difunctionalization
of
unsaturated
hydrocarbons
serves
as
an
efficient
means
to
rapidly
construct
molecular
skeletons
and
synthesize‐highly
valuable
compounds.
In
this
transformational
process,
diverse
positions
within
are
sequentially
functionalized
by
a
single
precursor
reagent,
thereby
achieving
highly
selective
transformations
that
promote
atom
economy.
Furthermore,
approach
minimizes
the
generation
numerous
byproducts
stemming
from
cross‐coupling
reactions
between
reactants,
owing
reduction
number
participating
components.
Therefore,
review
provides
in‐depth
analysis
utilizing
functional
reagent
in
recent
decades.
discussion
is
based
on
eight
different
classes
(carbon‐,
nitrogen‐,
phosphine‐,
oxygen‐,
sulfur‐,
selenium‐,
tellurium‐,
chlorine‐centered
radicals),
emphasizing
mechanism
specific
difunctionalization.
It
also
analyzes
detail
regulation
key
factors
such
regional
selectivity,
unique
insights
into
reaction
transformations.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 9, 2024
Abstract
A
direct
visible‐light‐promoted
radical‐triggered
tandem
cyclization
of
1,7‐diene
systems
with
cyclic
sulfonium
salts
by
using
copper(I)‐based
complexes
as
photoredox
catalyst
is
developed.
With
this
approach,
a
variety
sulfur‐containing
polycyclic
derivatives
are
prepared
through
alkylation/
6‐exo‐trig
cyclization/
5‐exo‐trig
under
mild
conditions.
In
addition,
the
photoinduced
copper‐catalyzed
ring‐opening
provides
alkyl
radical
intermediates,
which
prefers
addition
to
C−C
double
bond
that
connected
aromatic
ring
rather
than
electron‐deficient
vinyl
in
1,7‐dienes.
Moreover,
oxidation
desired
products
strategy
for
preparation
remote
nitrogen‐fused
substituted
sulfoxide
or
sulfone‐containing
derivatives.
Organic Letters,
Год журнала:
2024,
Номер
26(34), С. 7261 - 7266
Опубликована: Авг. 21, 2024
A
copper-catalyzed
trifluoromethylation
of
benzene-linked
1,7-dienes
with
1-trifluoromethyl-1,2-benziodoxole
via
a
radical
cascade
cyclization
process
for
the
synthesis
mono-
and
bis-trifluoromethylated
benzoxepines
is
developed.
The
selectivity
depends
on
substituents
double
bond
allyl
group
in
1,7-dienes.
large-scale
operation
late-stage
functionalization
bioactive
molecules
reveal
promising
utility
this
protocol.
Organic Letters,
Год журнала:
2023,
Номер
25(35), С. 6511 - 6516
Опубликована: Авг. 28, 2023
A
photoredox/Lewis
acid
cooperative
catalytic
system
has
been
developed
for
the
construction
of
Cvinyl–CRf
bonds
through
dehydrative
difluoroalkylation
benzyl
alcohols.
variety
allylic
gem-difluorides
could
be
obtained
in
moderate
yields
with
good
to
excellent
E/Z
selectivity.
In
addition,
several
control
experiments
have
explored,
and
a
possible
mechanism
was
proposed
this
process.
Abstract
A
new
preparatively
convenient
approach
to
the
synthesis
of
biopromising
1‐fluoroalkyl‐substituted
2,4,5,6‐tetrahydro‐1
H
‐imidazo[1,2‐
a
][1]benzazepines
has
been
developed,
based
on
chemoselective
photoreduction‐catalyzed
fluoroalkylation
cyclization
N
‐allyl‐4,5‐dihydro‐3
‐1‐benzazepin‐2‐amines
in
presence
fluorescein
as
an
organocatalyst.
The
use
comparatively
inexpensive
perfluoroalkyl
iodides
(R
f
I),
mild
reaction
conditions
and
wide
range
substituents
introduced
make
this
method
very
attractive
for
preparation
imidazobenzazepines
with
variety
fluorinated
moieties.
Abstract
A
metal‐free,
straightforward,
non‐hazardous
reagent‐added,
one‐pot
approach
for
the
efficient
synthesis
of
2‐arylimino‐2
H
‐chromenes
with
high
yields
was
developed
first
time
in
this
report
through
coupling
salicylaldehydes
β‐ketothioamides,
which
catalyzed
by
lipase
water.
This
green
strategy
provides
an
method
to
obtain
various
and
enriches
practical
application
biocatalysis.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(16), С. 11233 - 11243
Опубликована: Июль 25, 2024
A
visible-light-induced
radical
cascade
regioselective
acylation/cyclization
of
1,7-dienes
with
acyl
oxime
esters
for
the
preparation
acylation
polycyclic
compounds
via
NCR-mediated
C-C
σ-bond
cleavage
is
established.
The
transformation
involves
in
and
selective
addition
electron
neutral
C═C
bonds
synthesis
quinolinone
derivatives,
not
traditional
seven-membered
ring
products.
strategy
offers
several
advantages,
including
broad
substrate
tolerance,
no
need
bases,
hyperstoichiometric
initiators,
other
auxiliaries.
Organic Letters,
Год журнала:
2024,
Номер
26(41), С. 8832 - 8836
Опубликована: Окт. 9, 2024
A
nickel-catalyzed
tandem
alkoxylation/claisen
rearrangement
strategy
for
the
oxy-difluoroallylation
of
ynamides
has
been
developed.
In
this
reaction,
3,3-difluoroallyl
alcohol
was
used
as
a
fluorine-containing
building
block
to
construct
C–CF2
bond
first
time.
This
approach
is
recognized
its
robust
tolerance
functional
groups,
impressive
yields,
and
excellent
atomic
efficiency,
all
achieved
under
mild
reaction
conditions.
series
β,β-difluoromethyleneamide
derivatives
were
efficiently
obtained
through
simple
operations,
their
practicality
confirmed
gram-scale
synthesis
product
derivatization.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(12), С. 2516 - 2523
Опубликована: Янв. 1, 2023
An
unprecedented
(5
+
2)-cycloaddition
reaction
of
ortho-hydroxyethyl
phenol
and
internal
alkyne
was
developed.
This
Rh(III)-catalyzed
provided
benzoxepine
derivatives
which
have
very
high
biological
significance.
A
wide
range
phenols
alkynes
were
studied
to
provide
the
benzoxepines
in
yields.
