Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(6), P. 1154 - 1159
Published: Feb. 7, 2024
The
direct
functionalization
of
β-C(sp2)-H
bonds
in
enamides
has
garnered
increasing
attention
within
the
realm
organic
synthesis.
However,
these
remarkable
advancements
are
predominantly
dependent
on
transition
metals;
limited
success
been
achieved
via
organocatalytic
catalysis.
Herein,
we
report
a
CPA-catalyzed
cascade
intramolecular
cyclization
to
synthesize
chiral
dihydropyrimido[1,6-a]indoles
bearing
gem-difluoromethylene.
Moreover,
this
methodology
enables
synthesis
diverse
with
outstanding
enantioselectivities
moderate
high
yields.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(3)
Published: Nov. 2, 2023
With
the
rapid
development
of
asymmetric
catalysis,
demand
for
enantioselective
synthesis
complex
and
diverse
molecules
with
different
chiral
elements
is
increasing.
Owing
to
unique
features
atropisomerism,
catalytic
atropisomers
has
attracted
a
considerable
interest
from
chemical
science
community.
In
particular,
introducing
additional
elements,
such
as
carbon
centered
chirality,
heteroatomic
planar
helical
into
provides
an
opportunity
incorporate
new
properties
axially
compounds,
thus
expanding
potential
applications
atropisomers.
Thus,
it
important
perform
transformations
synthesize
bearing
multiple
elements.
spite
challenges
in
transformations,
recent
years,
chemists
have
devised
powerful
strategies
under
organocatalysis
or
metal
synthesizing
wide
range
enantioenriched
Therefore,
become
emerging
field.
This
review
summarizes
progress
this
field
indicates
challenges,
thereby
promoting
horizon.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: May 11, 2024
Abstract
The
exploration
of
the
complex
chemical
diversity
bicyclo[n.1.1]alkanes
and
their
use
as
benzene
bioisosteres
has
garnered
significant
attention
over
past
two
decades.
Regiodivergent
syntheses
thiabicyclo[4.1.1]octanes
(S‐BCOs)
highly
substituted
bicyclo[2.1.1]hexanes
(BCHs)
using
a
Lewis
acid‐catalyzed
formal
cycloaddition
bicyclobutanes
(BCBs)
3‐benzylideneindoline‐2‐thione
derivatives
have
been
established.
first
hetero‐(4+3)
BCBs,
catalyzed
by
Zn(OTf)
2
,
was
achieved
with
broad
substrate
scope
under
mild
conditions.
In
contrast,
less
electrophilic
BCB
ester
undergoes
Sc(OTf)
3
‐catalyzed
[2π+2σ]
reaction
1,1,2‐trisubstituted
alkenes,
yielding
BCHs
spirocyclic
quaternary
carbon
center.
Control
experiments
preliminary
theoretical
calculations
suggest
that
diastereoselective
product
formation
may
involve
concerted
between
zwitterionic
intermediate
E
‐1,1,2‐trisubstituted
alkenes.
Additionally,
nucleophilic
ring‐opening
mechanism.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 14, 2024
Photosynthesis,
converting
sustainable
solar
energy
into
chemical
energy,
has
emerged
as
a
promising
craft
to
achieve
diverse
organic
transformations
due
its
mild
reaction
conditions,
sustainability,
and
high
efficiency.
The
synthesis
of
sulfonated
compounds
drawn
significant
attention
in
the
pharmaceuticals,
agrochemicals,
materials
industries
unique
structure
electronic
properties
sulfonyl
groups.
Over
past
decades,
many
photocatalytic
sulfonylation
reactions
have
been
developed.
In
this
review,
recent
advances
photocatalyzed
reviewed
since
2020,
with
primary
focus
on
discussing
design
mechanism.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 23, 2024
Abstract
Catalytic
enantioselective
preparation
of
alkene
atropisomers
with
multiple
stereogenic
elements
and
discovery
their
applications
have
become
significant
but
challenging
issues
in
the
scientific
community
due
to
unique
structures
this
class
atropisomers.
We
herein
report
first
catalytic
atroposelective
cyclopentenyl[
b
]indoles,
a
new
kind
atropisomers,
point
axial
chirality
via
an
unusual
rearrangement
reaction
3‐indolylmethanols
under
asymmetric
organocatalysis.
Notably,
novel
type
promising
developing
chiral
ligands
or
organocatalysts,
discovering
antitumor
drug
candidates
fluorescence
imaging
materials.
Moreover,
theoretical
calculations
elucidated
possible
mechanism
non‐covalent
interactions
control
enantioselectivity.
This
approach
offers
synthetic
strategy
for
elements,
represents
3‐indolylmethanols,
which
will
advance
chemistry
indole
chemistry.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 20, 2025
Lewis
acid-enabled
reactions
of
donor-acceptor
cyclopropanes
(DACs)
with
indoline-2-thiones
are
reported.
The
reaction
exhibits
tunable
annulation
depending
on
the
acid
and
substituent
at
N1
indoline-2-thiones.
With
AlCl3
as
1-isopropylindoline-2-thiones
reactants,
a
direct
ring
opening
DACs,
followed
by
intramolecular
nucleophilic
addition/dehydration
takes
place
leading
to
formation
dihydro-2H-thiepino[2,3-b]indoles
in
moderate
good
yields.
Using
Yb(OTf)3
promoter
1-unsubstituted
(3
+
2)
cycloaddition
DACs
accompanied
sulfur
rearrangement
give
3-indolyl-4,5-dihydrothiophenes
In
addition,
synthetic
transformation
3-indolyl-4,5-dihydrothiophene
sulfone
indole-based
axially
chiral
scaffolds
further
extends
utility
structural
complexity.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 5796 - 5805
Published: March 25, 2025
The
transition
metal-catalyzed
asymmetric
[n
+
2]
cycloaddition
reaction
with
oxy-substituted
ketene
intermediates
remains
a
synthetic
challenge
due
to
the
limited
availability
of
suitable
precursors.
Herein,
we
report
visible-light-driven,
palladium-catalyzed
[4
vinyl
benzoxazinanones
siloxyketene
intermediates,
generating
structurally
diverse
chiral
quinolinone
derivatives
satisfactory
diastereo-
and
enantioselectivities.
transient
generation
siloxyketenes
from
α-ketoacylsilylanes
through
visible-light-induced
Brook
rearrangement
is
important
for
success
present
cycloaddition.
13C-labeling
experiments
reveal
pathway
involving
[1,3]-silyl
migration
process.
side
arm
effects
BOX
ligand
silyl
steric
hindrance
α-ketoacylsilanes
play
crucial
roles
in
stereoselectivity
control,
theoretical
calculations
provide
insights
into
stereochemical
outcome
reaction.
Chemical Synthesis,
Journal Year:
2023,
Volume and Issue:
3(1), P. 6 - 6
Published: Jan. 1, 2023
In
recent
years,
it
has
become
an
urgent
task
to
design
new
types
of
indole-based
platform
molecules
for
Nazarov-type
cyclizations
and
develop
organocatalytic
synthesizing
indole
derivatives.
To
fulfill
this
task,
in
work,
by
changing
the
alkynyl
terminal
substituent
from
t-Bu
aryl
group,
reactivity
3-alkynyl-2-indolylmethanols
is
modulated
serve
as
competent
substrates
Brønsted
acid-catalyzed
cyclization.
Based
on
reactivity,
first
cyclization
aryl-substituted
with
2-naphthols
accomplished,
leading
efficient
construction
a
class
axially
chiral
3,
4-dihydrocyclopenta[b]indole
scaffolds.
This
preliminary
investigation
asymmetric
provides
optional
strategy
atroposelective
cyclopenta[b]indole
addition,
preparation
optical
purity
established
through
resolution,
which
could
complementary
method
catalytic
approaches.
Acta Chimica Sinica,
Journal Year:
2023,
Volume and Issue:
81(7), P. 793 - 793
Published: Jan. 1, 2023
o-Hydroxyphenyl
substituted
p-quinone
methides
(p-QMs)
belong
to
a
class
of
p-QMs
with
unique
advantages.They
not
only
maintain
the
high
reactivity
p-QMs,
but
also
have
more
reactive
and
activation
sites
owing
introduction
hydroxyl
group.Therefore,
o-hydroxyphenyl
wide
applications
in
synthetic
medicinal
chemistry.The
catalytic
asymmetric
1,6-conjugate
addition
[4＋n]
cycloaddition
developed
very
rapidly
recent
years,
which
become
efficient
strategies
for
synthesis
chiral
oxygen-containing
heterocycles
arylmethanes
potential
bioactivity.This
review
summarizes
reactions
involving
points
out
remaining
challenges
this
research
area,
will
open
new
window
design
type
their
involved
reactions.
