Angewandte Chemie,
Год журнала:
2023,
Номер
135(51)
Опубликована: Ноя. 11, 2023
Abstract
Herein,
we
report
an
unprecedented
skeletal
rearrangement
reaction
of
tetrahydro‐
β
‐carbolines
enabled
by
copper‐catalyzed
single‐electron
oxidative
oxygenation,
in
which
H
2
O
and
act
as
oxygen
sources
to
generate
a
unique
2‐hydroxyl‐3‐peroxide
indoline
intermediate.
The
synthetic
reactivity
species
was
demonstrated
multi‐step
bond
cleavage
formation
cascade.
Using
readily
available
copper
catalyst
under
open‐air
conditions,
highly
important
yet
synthetically
difficult
spiro[pyrrolidone‐(3,1‐benzoxazine)]
products
were
obtained
single
operation.
utility
this
methodology
is
the
efficient
synthesis
natural
donaxanine
chimonamidine,
well
3‐hydroxyl‐pyrroloindoline
scaffold,
just
one
or
two
steps.
Organic Letters,
Год журнала:
2024,
Номер
26(2), С. 467 - 472
Опубликована: Янв. 5, 2024
Disclosed
here
is
a
visible-light
photoredox-catalyzed
intermolecular
sequential
α-aminomethyl/carboxylative
dearomatization
of
indoles
with
CO2
and
α-aminoalkyl
radical
precursors,
affording
series
functionalized
indoline-3-carboxylic
acids
lactams
in
good
yields
high
regioselectivity.
This
multicomponent
reaction
provides
green
facile
method
for
the
synthesis
diverse
indolines
by
using
as
carboxylic
carbonyl
source.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(30), С. 20904 - 20912
Опубликована: Июль 20, 2024
Although
divalent
Sm
reagents
are
some
of
the
most
important
single-electron
transfer
for
reductive
transformations,
their
catalytic
applications
challenging.
In
this
study,
a
bidentate
phosphine
oxide
ligand
substituted
with
9,10-diphenylanthracene
as
visible-light
antenna
was
designed
Sm-catalyzed
reduction
reactions
under
mild
reaction
conditions.
Pinacol
coupling
aryl
ketones
and
aldehydes
developed
1
mol
%
catalyst
organic
amine
(DIPEA)
sacrificial
reductant.
Mechanistic
studies
suggest
that
visible-light-antenna
coordinates
to
Sm(III)
reduces
Sm(II)
irradiation.
The
system
is
also
applicable
cross-pinacol
other
including
aza-pinacol
coupling,
flavone
dimerization,
C-O
bond
cleavage,
C-C
ring-opening
cyclopropane,
ketyl-olefin
cross-coupling
ketyl
radical
α-amino
radical.
Chemical Science,
Год журнала:
2024,
Номер
15(11), С. 4114 - 4120
Опубликована: Янв. 1, 2024
Starting
from
the
same
substrates,
tunable
C–H
functionalization
and
dearomatization
have
been
achieved
under
catalysis
of
a
new
organic
photocatalyst
–
isoazatruxene
ITN-2.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(35)
Опубликована: Июнь 12, 2024
Abstract
β‐Chiral
carboxylic
acids
and
their
derivatives
are
highly
valuable
structural
motifs
in
the
fields
of
asymmetric
synthesis
medicinal
chemistry.
However,
introduction
a
sterically
demanding
sidechain
to
β‐carbon,
such
as
an
all‐carbon
quaternary
center,
remains
significant
challenge
classical
polar
processes.
Recently,
N
‐heterocyclic
carbene
(NHC)
mediated
coupling
reactions
involving
persistent
ketyl
radicals
have
emerged
promising
strategy
assemble
crowded
carbon‐carbon
bonds.
Nevertheless,
achieving
enantioselectivity
these
challenging.
In
this
work,
we
report
our
recent
progress
controlling
for
relay
perfluoroalkyl
vinylogous
radicals.
We
developed
chiral
bifunctional
NHC‐squaramide
catalyst
that
achieves
high
facial
selectivity
critical
bond‐forming
event
congested
tertiary
carbon
radical
radical.
Chiral
carboxylates
bearing
center
at
β‐position
can
be
prepared
good
yield
excellent
enantiomeric
excess.
Results
from
density
functional
theory
(DFT)
calculations
nuclear
Overhauser
effect
(NOE)
experiments
indicate
,
N’
‐diaryl
squaramide
motif
adopts
unusual
syn
‐
conformation,
enabling
hydrogen
bonding
interactions
with
enolate
oxygen,
thereby
rigidifying
overall
conformation
transition
state.
Molbank,
Год журнала:
2025,
Номер
2025(1), С. M1962 - M1962
Опубликована: Фев. 5, 2025
(1S,1′S)-2,2′-(Benzylazanediyl)bis(1-((3aR,4R,6aR)-2,2-dimethyltetrahydrofuro
[3,4
d][1,3]dioxol-4-yl)ethan-1-ol),
presenting
a
tertiary
β-aminodiol
moiety,
was
synthesized
in
72%
yield
one-step
reaction
from
an
aminolysis
of
isosorbide-derived
oxirane
with
benzylamine.
This
fully
characterized
by
1H
and
13C
NMR
HRMS
analyses.
ACS Central Science,
Год журнала:
2025,
Номер
11(5), С. 805 - 815
Опубликована: Май 2, 2025
Significant
advancements
have
been
made
in
the
catalytic
asymmetric
dearomatization
of
indoles
for
constructing
valuable
chiral
polycyclic
N-heterocycles.
However,
dearomative
cyclopropanation
continues
to
pose
a
formidable
challenge.
Furthermore,
diverse
transformations
indoline-fused
cyclopropanes
via
strain
release
remain
largely
unexplored,
potentially
unveiling
new
chemistry.
Here,
we
disclose
Cu-catalyzed
indole-diynes
and
subsequent
[3
+
2]
cycloaddition
with
oxygen,
facilitating
divergent
atom-economical
synthesis
enantioenriched
cyclopropane-
1,2-dioxolane-fused
indolines
moderate
excellent
yields
generally
outstanding
diastereo-
enantioselectivities
broad
substrate
scope.
Importantly,
this
protocol
not
only
represents
first
utilizing
alkynes
as
carbene
precursors
but
also
constitutes
construction
1,2-dioxolanes
high
stereoselectivity.
Interestingly,
Brønsted
acid-promoted
ring-opening
rearrangement
cyclopropane-fused
display
distinctive
chemoselectivity
afford
cyclohepta-[b]-indoles
good
efficiency
enantiocontrol.
In
addition,
both
potential
reaction
pathways
origins
control
within
tandem
sequence
are
robustly
supported
by
experiments
theoretical
calculations.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(51)
Опубликована: Ноя. 11, 2023
Herein,
we
report
an
unprecedented
skeletal
rearrangement
reaction
of
tetrahydro-β-carbolines
enabled
by
copper-catalyzed
single-electron
oxidative
oxygenation,
in
which
H2
O
and
O2
act
as
oxygen
sources
to
generate
a
unique
2-hydroxyl-3-peroxide
indoline
intermediate.
The
synthetic
reactivity
species
was
demonstrated
multi-step
bond
cleavage
formation
cascade.
Using
readily
available
copper
catalyst
under
open-air
conditions,
highly
important
yet
synthetically
difficult
spiro[pyrrolidone-(3,1-benzoxazine)]
products
were
obtained
single
operation.
utility
this
methodology
is
the
efficient
synthesis
natural
donaxanine
chimonamidine,
well
3-hydroxyl-pyrroloindoline
scaffold,
just
one
or
two
steps.
