Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(25), С. 5014 - 5031
Опубликована: Янв. 1, 2024
Transition
metal
catalyzed
C-H
bond
activation
has
become
one
of
the
most
important
tools
for
constructing
new
chemical
bonds.
Introducing
directing
groups
to
substrates
is
key
a
successful
reaction,
these
can
also
be
further
transformed
in
reaction.
Amidines
with
their
unique
structure
and
reactivity
are
ideal
transition
metal-catalyzed
transformations.
This
review
describes
major
advances
mechanistic
investigations
activation/annulation
tandem
reactions
amidines
until
early
2024,
focusing
on
unsaturated
compounds,
such
as
alkynes,
ketone,
vinylene
carbonate,
cyclopropanols
derivatives.
Meanwhile
this
manuscript
explores
reaction
different
carbene
precursors,
example
diazo
azide,
triazoles,
pyriodotriazoles,
sulfoxonium
ylides
well
own
activation/cyclization
reactions.
A
bright
outlook
provided
at
end
manuscript.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(6), С. 834 - 853
Опубликована: Янв. 25, 2023
Semipinacol
rearrangement
has
brought
several
elegant
methods
for
the
rapid
synthesis
of
various
complex
scaffolds
and
as
a
result,
been
applied
extensively
in
total
natural
products.
Apart
from
classical
ways,
where
transition
metal
or
acids
catalyzes
formation
carbocation,
semipinacol
seen
numerous
revolutions
now
are
being
happening
an
eco-friendly
manner
relying
on
catalytic
radical-polar
crossover
tool.
These
processes
mainly
occurring
through
photocatalysis
electrocatalysis.
This
review
will
provide
brief
idea
these
developments.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(32)
Опубликована: Апрель 4, 2024
Abstract
Highly
regioselective
C−H
alkylation
reactions
of
tertiary
anilines
and
alkyl
amines
with
simple
alkenes
have
been
achieved
by
the
use
imidazolin‐2‐iminato
scandium
complexes.
This
protocol
provided
an
efficient
atom‐economical
route
to
structurally
diverse
amine
derivatives.
The
basic
ligand,
a
coordinating
THF
in
catalyst
substitution
alkene
substrates
were
found
switch
regioselectivity
presumably
due
generation
different
types
catalytically
active
species
or
formation
relatively
stable
intermediates.
On
basis
deuterium
labeling
experiments
KIE
experiments,
possible
catalytical
cycles
understand
reaction
mechanism
as
well
regioselectivity.
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.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1422 - 1430
Опубликована: Янв. 9, 2025
The
electrochemical
methods
for
asymmetric
indolization
are
still
elusive
and
pose
a
significant
challenge.
Taking
advantage
of
2-alkynylanilines
as
electrochemically
compatible
indolyl
equivalents,
we
herein
represent
mild
highly
enantioselective
electrocatalytic
process
tandem
C–H
to
form
2,3′-biindolyl
atropisomers
along
with
hydrogen
evolution
reaction.
Integrated
experimental
computational
mechanistic
studies
revealed
that
sequential
metalation/nucleophilic
cyclization/reductive
elimination/anodic
oxidation
sequence
involving
RhIII–RhI–RhIII
catalytic
cycle
accounts
the
established
transformation.
Presented
herein
is
a
nickel-catalyzed
chemo-
and
regioselective
three-component
tandem
carboamination
cyclization
of
terminal
alkynes
with
organoboronic
acids
anthranils
for
facile
modular
access
to
2,3-substituted
quinolines.
In
this
process,
anthranil
has
dual
roles:
serving
as
an
electrophilic
aminating
reagent
redox
buffer
suppress
the
generation
off-cycle
Ni(0)
complex.
Moreover,
anionic
acetylacetonate
(acac)
ligand
was
found
be
vital
ensure
productive
Ni(I)-Ni(III)-Ni(I)
catalytic
cycle.
We
report
a
metal-free
synthesis
of
highly
functionalized
1,6-amino
alcohols
through
visible-light
1,2-carboimination
alkenes
and
bifunctional
starting
materials
prepared
from
commercially
available
alcohols.
This
protocol
orchestrates
the
generation
up
to
four
different
types
radicals,
which
are
efficiently
recombined
yield
1,6-iminyl
The
methodology
demonstrated
broad
functional
group
tolerance
was
validated
by
late-stage
installation
alcohol
motif
in
biomolecules
pharmaceuticals
scale-up
process.
versatility
products
highlighted
their
conversion
into
variety
useful
intermediates
for
target-directed
synthesis.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 8, 2024
Palladium
catalyzed
tandem
reaction
represents
a
one-pot
synthetic
approach
to
efficiently
synthesize
complex
functionalized
molecules
while
reducing
steps,
aligning
with
the
principles
of
green
chemistry.
However,
achieving
direct
cascade
aza-Wacker
and
Povarov
reactions
in
synthesis
presents
challenge
due
substrate
compatibility
issues
between
two
reactions.
In
this
work,
we
describe
an
aza-Wacker/Povarov
employing
highly
electrophilic
palladium
catalyst,
which
effectively
converts
anilines
1,6-dienes
into
hexahydro-cyclopenta[b]quinolines.
The
optimized
conditions
yield
up
79%,
diastereoselectivity
>
20:1.
Substrate
range
testing
reveals
various
sensitive
functional
groups,
successful
late-stage
modifications
are
performed
on
several
natural
products
drug
molecules,
demonstrating
versatility
practicality
method.
Additionally,
preliminary
investigation
mechanism
suggests
process
followed
by
process.
