The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 20, 2025
The
acid-controlled
single-component
retro-aldol/Michael
addition
cascade
reaction
and
[4
+
2]
cycloaddition
of
benzofuran-derived
azadienes
(BDAs)
are
reported
for
the
first
time.
Under
conditions
trifluoromethanesulfonic
acid
as
catalyst
with
water,
BDAs
initiate
retro-aldol
reaction,
followed
by
a
1,4-Michael
addition,
yielding
(arylmethylene)bis(dibenzofuran)
products
excellent
yields
broad
substrate
applicability.
This
represents
application
in
reaction.
In
contrast,
absence
water
boron
trifluoride
etherate
catalyst,
undergo
constructing
spiro[benzofuran-2,3'-benzofuro[3,2-b]pyridine]
framework
high
diastereoselectivity.
method
features
mild
atom
economy,
provides
new
approach
benzofuran
scaffold
derivatives.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(10), P. 4146 - 4174
Published: Jan. 1, 2022
The
advances
on
metal-catalysed
high-order
dipolar
annulations
were
comprehensively
summarized
in
this
review.
To
further
exploit
the
potential
of
unique
annulation
strategy,
a
research
outlook
was
also
proposed.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 883 - 971
Published: Dec. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(24)
Published: March 28, 2022
gem-Difluoromethylene
moieties
are
attractive
in
medicinal
chemistry
due
to
their
ability
mimic
other
more
ubiquitous
functional
groups.
Thus,
effective
asymmetric
methods
for
construction
highly
desirable,
especially
the
industrial
production
of
chiral
drugs.
Using
a
Pd-catalyzed
[4+2]
cycloaddition
between
substituted-2-alkylidenetrimethylene
carbonates
and
gem-difluoroalkyl
ketones,
we
were
able
easily
access
1,3-dioxanes
that
contain
tetrasubstituted
difluoroalkyl
stereogenic
center
cyclic
acyclic
skeletons.
A
novel
phosphoramidite
ligand,
which
contains
bulky
1,1-dinaphthylmethanamino
moiety,
was
developed
provide
products
high
yield
with
excellent
enantio-,
diastereo-,
regioselectivity.
Strikingly,
gem-difluoro
substitution
pattern
promotes
reaction,
pentafluoroethylketone,
an
α,α-difluorinated
β-ketoester,
β-ketosulfone
suitable
substrates
this
method.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
22(1), P. 37 - 54
Published: Nov. 27, 2023
Developing
efficient
and
straightforward
strategies
to
rapidly
construct
structurally
distinct
diverse
organic
molecules
is
one
of
the
most
fundamental
tasks
in
synthesis,
drug
discovery
materials
science.
In
recent
years,
divergent
synthesis
functional
from
same
starting
has
attracted
significant
attention
been
recognized
as
an
powerful
strategy.
To
achieve
this
objective,
proper
adjustment
reaction
conditions,
such
catalysts,
solvents,
ligands,
etc.,
required.
review,
we
summarized
efforts
chemo-,
regio-
stereodivergent
reactions
involving
acyclic
cyclic
systems
catalyzed
by
palladium
complexes.
Meanwhile,
types,
including
carbonylative
reactions,
coupling
cycloaddition
well
probable
mechanism
have
also
highlighted
detail.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(6)
Published: Dec. 15, 2023
Abstract
We
report
herein
an
unprecedented
enantioselective
(4+4)
cycloaddition
of
simple
1,3‐dienes
with
azadienes
for
the
construction
fused
eight‐membered
N
‐heterocycles.
In
this
transformation,
π‐Lewis
basic
Pd(0)
catalyst
achieves
activation
to
induce
nucleophilic
addition
followed
by
ring
cyclization
via
a
selective
terminal
allylic
substitution.
Furthermore,
highly
efficient
and
diastereoselective
derivatizations
rings
provide
facile
access
diverse
enantiopure
tetra‐
hexacyclic
compounds
potential
application
in
medicinal
chemistry.
Chinese Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
42(10), P. 3051 - 3051
Published: Jan. 1, 2022
Chiral
heterocyclic
compounds
are
an
important
class
of
chiral
substances,
which
widespread
in
many
drugs,
pesticides
and
catalysts.Therefore,
the
efficient
asymmetric
synthesis
these
becomes
a
research
hotspot
organic
synthesis.Transition
metal-catalyzed
cyclization
with
heteroatom-dipole
precursors
is
method
to
construct
frameworks.Among
them,
designed
based
on
transition
allyl
or
propargyl
substitutions
have
been
extensively
studied
past
two
decades
occupied
role
this
field.The
cyclizations
introduced
detail.The
advantages
existing
problems
current
methods
analyzed,
would
provide
useful
reference
for
researchers
related
fields.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(12), P. 2060 - 2066
Published: May 5, 2022
Abstract
A
palladium‐catalyzed
[4+2]
cycloaddition
of
hydroxy‐tethered
allyl
carbonates
with
five
types
electron‐deficient
alkenes
has
been
achieved,
in
which
a
type
new
acted
as
valuable
precursors
for
the
formation
1,4‐C,O‐dipole
allylpalladium
intermediates.
The
reaction
proceeded
efficiently
under
mild
conditions
to
provide
corresponding
tetrahydropyran
derivatives
moderate
high
yields
excellent
diastereoselectivities.
magnified
image
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(50), P. 9205 - 9209
Published: Dec. 12, 2022
We
developed
novel
shackled
P-chiral
ligands
based
on
1-phosphanorbornenes
and
oxazolines.
They
were
subsequently
evaluated
in
palladium-catalyzed
(4+2)
annulations,
producing
enantioenriched
tetrahydropyran
scaffolds
good
yields
with
high
site
selectivity
enantioselectivity.
Moreover,
chemoselective
(4+4)
products
also
achieved
by
using
acyclic
imines.
In
addition,
density
functional
theory
calculations
performed
to
afford
the
energy
profile
of
Michael
addition
step
ring
formation
step.
This
demonstrated
that
enantioselective
annulations
reaction
between
mostly
under
thermodynamic
control.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(21), P. 2825 - 2831
Published: June 25, 2023
Comprehensive
Summary
We
developed
a
novel
Pd‐catalyzed
[4
+
4]
cycloaddition
of
(benzo)furan‐derived
azadienes
with
homo‐TMM
all‐carbon
1,4‐dipoles
in
situ
generated
from
α
‐allyl
malonate
derivatives,
affording
an
array
benzofuro[3,2‐
b
]azocines
and
furo[3,2‐
good
to
excellent
yields
(up
96%)
exclusive
regioselectivities.
This
methodology
featured
mild
reaction
conditions
functional
group
tolerance.
The
synthetic
utility
was
demonstrated
by
gram‐scale
reaction.
Furthermore,
the
catalytic
asymmetric
version
has
also
been
explored.
