Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 22, 2025
The
synthesis
of
chiral
tetrahydroquinolines
(THQs)
has
garnered
significant
interest
from
medicinal
chemists
due
to
their
frequent
presence
as
pharmacophores
in
bioactive
compounds.
While
existing
synthetic
methods
have
primarily
focused
on
THQs
with
single
or
multiple
endocyclic
centers,
the
selective
construction
both
endo-
and
exo-cyclic
centers
remains
a
challenge
that
requires
further
development.
This
study
introduces
dynamic
kinetic
resolution
(DKR)-based
transfer
hydrogenation
racemic
2-substituted
quinolines,
which
yields
structurally
novel
consecutive
excellent
stereoselectivities
(59
examples,
generally
>20:1
dr
>90%
ee,
up
three
stereocenters).
Our
approach
offers
mechanistically
method
for
asymmetric
transformation
electron-deficient
aromatic
N-heterocycles
presents
an
innovative
way
expand
N-heterocycle
chemical
space
chemistry.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(12), P. 6600 - 6624
Published: Jan. 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.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
ConspectusN-Heterocycles
are
essential
in
pharmaceutical
engineering,
materials
science,
and
synthetic
chemistry.
Recently,
skeletal
editing,
which
involves
making
specific
point
changes
to
the
core
of
a
molecule
through
single-atom
insertion,
deletion,
or
transmutation,
has
gained
attention
for
its
potential
modify
complex
substrates.
In
this
context,
insertion
nitrogen
atoms
into
carbocycles
form
N-heterocycles
emerged
as
significant
research
focus
modern
chemistry
owing
novel
logic.
This
distinctive
retrosynthetic
approach
enables
late-stage
modification
molecular
skeletons
provides
different
pathway
synthesizing
multiply
substituted
N-heterocycles.
Nevertheless,
atom
proven
challenging
because
inherent
inertness
carbon-based
difficulty
cleaving
C-C
bonds.
Therefore,
selective
editing
remains
growing
field
Account
primarily
highlights
contributions
our
laboratory
active
acknowledges
key
from
other
researchers.
It
is
organized
two
sections
based
on
type
carbocycle.
The
first
section
explores
cycloalkenes.
Recent
Co-catalyzed
oxidative
azidation
strategies
have
enabled
cyclobutenes,
cyclopentenes,
cyclohexenes,
facilitating
synthesis
polysubstituted
pyridines,
been
conventionally
pyridine
cross-coupling.
subsequent
discovery
realm
arenes.
site-selective
stable
arenes
We
developed
method
intramolecular
benzene
rings
2-amino
biaryls
by
suppressing
competing
C-H
process
using
paddlewheel
dirhodium
catalyst.
addition,
address
issues
we
employed
arenols
substrates,
could
act
controlling
elements
editing.
reported
Cu-catalyzed
arenols,
proceeds
dearomative
azidation/aryl
migration
process,
enabling
incorporation
Inspired
result,
recently
extended
reaction
model
Fe-catalyst
facilitate
ring
contraction
nitrogen-inserted
product,
achieving
carbon-to-nitrogen
transmutation
arenols.
Various
polyaromatic
effectively
undergo
desired
atom's
presenting
considerable
various
applications
Account,
present
an
overview
achievements
reactions,
with
scopes,
mechanistic
features,
applications.
anticipate
that
will
provide
valuable
insights
propel
development
innovative
methodologies
both
N-heterocycle
synthesis.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3419 - 3429
Published: Feb. 16, 2024
Herein,
we
describe
a
dual
photocatalytic
system
to
synthesize
phenol–pyridinium
salts
using
visible
light.
Utilizing
both
electron
donor–acceptor
(EDA)
complex
and
iridium(III)
cycles,
the
C–N
cross-coupling
of
unprotected
phenols
pyridines
proceeds
in
presence
oxygen
furnish
pyridinium
salts.
Photocatalytic
generation
phenoxyl
radical
cations
also
enabled
nucleophilic
aromatic
substitution
(SNAr)
fluorophenol
with
an
electron-poor
pyridine.
Spectroscopic
experiments
were
conducted
probe
mechanism
reaction
selectivity.
The
unique
reactivity
these
displayed
several
derivatization
reactions,
providing
rapid
access
diverse
chemical
space.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 8, 2025
We
report
the
first
example
of
dearomative
(3
+
2)
cycloadditions
3-nitro(aza)-indole,
-benzofuran,
and
-benzothiophene
derivatives
in
presence
allenyl
sulfones,
using
sulfinate
ammonium
ion
pairs
as
organocatalytic
promoters.
The
methodology
provides
a
new,
facile,
efficient
protocol
for
synthesis
functionalized
2,3-fused
cyclopentannulated
indolines
dihydrobenzofurans.
Molecules,
Journal Year:
2024,
Volume and Issue:
29(9), P. 1920 - 1920
Published: April 23, 2024
Skeleton
editing
has
rapidly
advanced
as
a
synthetic
methodology
in
recent
years,
significantly
streamlining
the
synthesis
process
and
gaining
widespread
acceptance
drug
development.
This
field
encompasses
diverse
ring
reactions,
many
of
which
exhibit
immense
potential
skeleton
editing,
facilitating
generation
novel
skeletons.
Notably,
reactions
that
involve
cleavage
two
distinct
rings
followed
by
reformation
new
through
insertion
play
pivotal
role
construction
article
aims
to
compile
systematize
this
category
emphasizing
primary
reaction
types
offering
thorough
exploration
their
associated
complexities
challenges.
Our
endeavor
is
furnish
readers
with
comprehensive
strategies,
igniting
research
interest
injecting
fresh
impetus
into
advancement
domain.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: May 28, 2024
Dearomative
construction
of
multiply-fused
2D/3D
frameworks,
composed
aromatic
two-dimensional
(2D)
rings
and
saturated
three-dimensional
(3D)
rings,
from
readily
available
quinolines
has
greatly
contributed
to
drug
discovery.
However,
dearomative
cycloadditions
in
the
presence
photocatalysts
usually
afford
5,6,7,8-tetrahydroquinoline
(THQ)-based
polycycles,
access
1,2,3,4-THQ-based
structures
remains
limited.
Herein,
we
present
a
chemo-,
regio-,
diastereo-,
enantioselective
transformation
into
6-6-4-membered
without
any
catalyst,
through
combination
nucleophilic
addition
borate-mediated
[2+2]
photocycloaddition.
Detailed
mechanistic
studies
revealed
that
photoexcited
borate
complex,
generated
quinoline,
organolithium,
HB(pin),
accelerates
cycloaddition
suppresses
rearomatization
occurs
conventional
Based
on
our
analysis,
also
developed
further
photoinduced
affording
other
types
frameworks
isoquinoline
phenanthrene.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(45), P. 9752 - 9758
Published: Nov. 6, 2024
We
developed
a
protocol
for
the
synthesis
of
functionalized
pyrrolo[2,1-a]isoquinoline
derivatives
(PIQDs)
3
from
enaminones
1
using
vinylene
carbonate
2.
This
strategy
involved
[3
+
2]
and
[4
cycloadditions
via
heating
mixture
substrates
with
2
DCE
at
60
°C,
catalyzed
by
[Cp*RhCl2]2
oxidized
Cu(OAc)2
AgSbF6
promoted
NaOAc.
As
we
increased
reaction
temperature
to
110
°C
under
same
conditions,
synthesized
PIQDs
4
through
sequential
C–H
activation,
alkene
insertion,
migratory
C–N
reductive
elimination,
β-O
finally
dehydration.
result,
series
3–4
were
generated
forming
four
bonds
(2
C–C
bonds)
in
single
step.
realizes
linear
molecules
potential
biological
activity,
specifically
natural-like
heterocycles
(3–4).
It
expands
application
as
C2
synthon
construction
pyrrole
isoquinoline
skeletons
combinatorial
parallel
syntheses
one-pot
reactions.
