Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
13(1)
Published: Dec. 11, 2023
Abstract
This
study
reports
the
first
synthesis
of
tetrahydroquinaldic
and
tetrahydropicolinic
amides
using
readily
available
quinolines
pyridines
through
dearomative
difunctionalization
hydrolysis
under
transition‐metal‐
reductant‐free
conditions.
The
prepared
amide
products
could
be
easily
oxidized
to
corresponding
quinaldic
picolinic
amides.
Furthermore,
chemical
reactivity
group
has
been
explored
develop
convenient
methods
for
their
conversion
other
common
organic
functional
groups.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: July 3, 2023
Abstract
Herein,
we
report
a
one‐pot
method
for
enantioselective
C−H
allylation
of
pyridines
at
C3
via
tandem
borane
and
palladium
catalysis.
This
involves
borane‐catalyzed
pyridine
hydroboration
to
generate
dihydropyridines,
then
palladium‐catalyzed
the
dihydropyridines
with
allylic
esters,
finally
air
oxidation
allylated
afford
products.
enables
introduction
an
group
excellent
regio‐
enantioselectivities.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2358 - 2363
Published: Jan. 17, 2024
Dearomatization
of
pyridines
is
a
well-established
synthetic
approach
to
access
piperidines.
Although
remarkably
powerful,
existing
dearomatization
processes
have
been
limited
the
hydrogenation
or
addition
carbon-based
nucleophiles
activated
pyridiniums.
Here,
we
show
that
arenophile-mediated
dearomatizations
can
be
applied
directly
introduce
heteroatom
functionalities
without
prior
substrate
activation.
The
arenophile
platform
in
combination
with
olefin
oxidation
chemistry
provides
dihydropyridine
cis-diols
and
epoxides.
These
previously
elusive
compounds
are
now
readily
accessible
used
for
downstream
preparation
diversely
functionalized
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(4), P. 1936 - 1983
Published: Jan. 1, 2024
This
review
analyses
recent
advances
and
strategies
employed
in
the
Pd-AAA
of
nucleophilic
prochiral
heterocycles.
Each
section
is
focused
on
a
specific
heterocycle,
where
optimisation
data
reaction
scope
have
been
carefully
analysed.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
ConspectusDearomatization
of
simple
aromatics
serves
as
one
the
most
direct
strategies
for
converting
abundant
chemical
feedstocks
into
three-dimensional
value-added
products.
Among
such
transformations,
cycloadditions
between
arenes
and
alkenes
have
historically
offered
effective
means
to
construct
complex
polycyclic
architectures.
However,
traditionally
harsh
conditions,
high-energy
UV
light
irradiation,
greatly
limited
scope
this
transformation.
Nevertheless,
recent
progress
has
led
development
visible-light-promoted
dearomative
photocycloadditions
with
expanded
capable
preparing
bicyclic
structures.A
fundamentally
distinct
approach
involves
visible-light
activation
arenophiles,
which
undergo
para-photocycloaddition
various
aromatic
compounds
produce
arene-arenophile
cycloadducts.
While
only
transiently
stable
subject
retro-cycloaddition,
further
functionalization
photocycloadducts
allowed
a
wide
collection
dearomatization
methodologies
that
access
products
orthogonal
existing
biological
processes.
Central
strategy
was
observation
photocycloaddition
reveals
π-system
can
be
functionalized
through
traditional
olefin
chemistry.
Coupled
subsequent
[4
+
2]-cycloreversion
arenophile,
process
acts
effectively
isolate
single
from
an
ring.
We
developed
several
transformations
bias
methodology
perform
single-atom
insertion
π-extension
reactions
prepare
unique
cannot
prepared
easily
means.Through
application
epoxidation,
we
were
able
develop
method
epoxidation
pyridines
arene-oxides
pyridine-oxides,
respectively.
Notably,
when
arenophile
chemistry
is
applied
arenes,
transposed
site
native
olefinic
reactivity,
enabling
site-selectivity
functionalization.
As
result,
oxygen
(aza)arenes
3-benzoxepines.
When
applying
in
context
cyclopropanations,
accomplish
cyclopropanation
yield
benzocycloheptatrienes
upon
cycloreversion.
while
Buchner
ring
expansion
powerful
carbon
corresponding
does
not
ring-expanded
Furthermore,
could
utilized
synthesis
novel
nanographenes
M-region
annulative
(M-APEX)
reaction.
Traditionally,
methods
rely
on
reactivity
at
K-
bay-region.
arenophiles
activate
reactivity.
arenophile-mediated
diarylation,
followed
by
cycloreversion,
deliver
π-extended
exclusive
selectivity.
Inorganic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 4336 - 4346
Published: Jan. 1, 2024
Low-coordinate
dimeric
Ca(
ii
)
and
Yb(
hydrides
{[
t
Bu
2
CarbAr
]MH(THF)}
]MH(η
6
-C
7
H
8
)}
efficiently
catalyze
PhSiH
3
addition
to
pyridines
at
ambient
T
.
At
90°
C
the
same
complex
catalyzes
reverse
reaction.
Molecules,
Journal Year:
2024,
Volume and Issue:
29(22), P. 5265 - 5265
Published: Nov. 7, 2024
Sequential
Pd-catalyzed
one-pot
synthetic
methodologies
have
emerged
as
a
powerful
and
versatile
approach
in
organic
synthesis,
enabling
the
construction
of
complex
heterocyclic
architectures
with
high
efficiency,
selectivity,
atom
economy.
This
review
discusses
key
advancements
multistep,
sequentially
processes
for
accessing
derivatives,
focusing
on
classic
reactions
like
Suzuki-Miyaura,
Sonogashira,
Heck,
hydroamination
extending
to
specialized
techniques
such
directed
C-H
activation.
The
concatenation
these
steps
has
advanced
scope
strategies.
A
section
is
dedicated
exploring
cooperative
use
palladium
other
metals,
particularly
copper,
ruthenium,
gold,
which
broadened
range
accessible
derivatives.
Highlighted
applications
include
synthesis
biologically
pharmaceutically
relevant
compounds,
tris(hetero)aryl
systems,
spiro-oxindoles,
indole
These
strategies
not
only
streamline
but
also
align
green
chemistry
principles
by
minimizing
purification
reducing
waste
energy
consumption.
addresses
current
challenges
limitations
methodologies,
offering
insights
into
ongoing
efforts
optimize
reaction
conditions
expand
applicability
sequential
processes.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Oct. 20, 2023
Nitrogen
heterocycles
play
a
vital
role
in
pharmaceuticals
and
natural
products,
with
the
six-membered
aromatic
aliphatic
architectures
being
commonly
used.
While
synthetic
methods
for
N-heterocycles
are
well-established,
synthesis
of
their
functionalized
analogues,
particularly
piperidine
derivatives,
poses
significant
challenge.
In
that
regard,
we
propose
stepwise
dearomative
functionalization
reaction
construction
highly
decorated
derivatives
diverse
functional
handles.
We
also
discuss
challenges
related
to
site-selectivity,
regio-
diastereoselectivity,
provide
insights
into
mechanism
through
mechanistic
studies
density
theory
computations.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3582 - 3595
Published: Feb. 20, 2024
Selective
cascading
hydroelementation
of
N-heteroarenes
represented
by
pyridines
can
provide
diverse
accesses
to
not
only
dihydro
products
but
also
tetrahydro
and
piperidines
bearing
an
sp3
C–E
bond
(E
=
B,
Si,
etc.).
Herein,
we
describe
the
Co-catalyzed
hydroboration
quinolines
pyridines.
A
precatalyst
Co(acac)2
with
a
P∧N
ligand
(R-Fc-PHOX;
R
tBu,
Ph,
or
iPr)
enabled
stepwise
HBpin
(1
3
equiv)
exclusively
give
1,2-DHQ
C4-borylated
tetrahydroquinolines
in
high
efficiency
(TON
up
2000/[Co]
gram
scale
TOF
500/h).
similar
system
using
monodentate
phosphine
efficiently
catalyzed
regio-
stereoselective
double
furnish
range
1,3-diboryl-1,2,3,4-tetrahydropyridines,
which
were
situ
hydrogenated
corresponding
C–B
β
nitrogen
atom.
Experimental
mechanistic
studies
on
quinoline
suggested
insights
as
follows:
(1)
precursor
active
(P∧N)Co
hydride
species
is
(P∧N)Co(acac)2,
involved
catalyst
initiation
step
induction
period.
(2)
The
first
phase
highly
1,2-selective.
(3)
C(sp3)–B
formation
second
turnover-limiting
overall
catalytic
process.
(4)
under
kinetic
differentiation.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2309 - 2314
Published: March 11, 2024
2-Alkylpyridines
are
a
privileged
scaffold
throughout
the
realm
of
organic
synthesis
and
play
key
role
in
natural
products,
pharmaceuticals,
agrochemicals.
Herein,
we
report
first
B-alkyl
Suzuki
cross-coupling
2-pyridyl
ammonium
salts
to
access
functionalized
2-alkylpyridines.
The
use
well-defined,
operationally
simple
Pd-NHCs
permits
for
an
exceptionally
broad
scope
challenging
C–N
with
organoboranes
containing
β-hydrogen,
representing
novel
method
discovery
highly
sought-after
molecules
plant
protection.
Synthesis,
Journal Year:
2024,
Volume and Issue:
56(22), P. 3349 - 3364
Published: March 5, 2024
Abstract
Transition-metal-catalyzed
asymmetric
allylic
substitution
reactions
represent
a
hot
research
topic
in
the
field
of
synthesis,
with
significant
progress
having
been
made.
Among
diverse
catalysis
systems,
relay
enables
sequential
activation
multiple
steps
one
pot
and
rapid
construction
chiral
centers,
providing
simple
powerful
platform
for
organic
synthesis.
Recently,
has
successfully
applied
to
reactions,
variety
challenging
transformations
have
realized.
This
Short
Review
summarizes
related
on
based
over
last
decade.
1
Introduction
2
The
General
Transformation
Model
3
Allylation
Relays
Further
Reaction
4
Initial
5
Conclusion
Outlook
