We
herein
report
the
serendipitous
discovery
of
interrupted
Plancher
rearrangement
initiated
by
an
HFIP-promoted
dearomative
epoxide-indole
cyclization,
unlocking
a
new
blueprint
to
formal
C3
umpolung
reactivity
indoles.
This
rapid
complexity
generating
cascade
process
paves
way
toward
class
fused-bridged
indolines
in
high
yields
and
under
full
regio-
diastereocontrol.
The
reaction
is
amenable
wide
range
substituents
starting
materials.
Organic Letters,
Год журнала:
2023,
Номер
25(39), С. 7214 - 7219
Опубликована: Сен. 26, 2023
A
novel
Rh(III)-catalyzed
cascade
alkenyl
C-H
activation/[3
+
2]
annulation/pinacol
rearrangement
reaction
of
enaminones
with
iodonium
ylides
has
been
developed.
This
methodology
provides
a
new
and
straightforward
synthetic
strategy
to
afford
highly
functionalized
2-spirocyclo-pyrrol-3-ones
in
satisfactory
yield
from
readily
available
starting
materials
under
mild
conditions.
Moreover,
gram-scale
reactions
further
derivatization
experiments
are
implemented
demonstrate
the
potential
utility
this
developed
approach.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(26)
Опубликована: Апрель 20, 2024
Photoinduced
Pd-catalyzed
bisfunctionalization
of
butadienes
with
a
readily
available
organic
halide
and
nucleophile
represents
an
emerging
attractive
method
to
assemble
versatile
alkenes
bearing
various
functional
groups
at
the
allylic
position.
However,
enantiocontrol
and/or
diastereocontrol
in
C-C
or
C-X
bond-formation
step
have
not
been
solved
due
open-shell
process.
Herein,
we
present
cascade
asymmetric
dearomatization
reaction
indoles
via
photoexcited
1,2-biscarbonfunctionalization
1,3-butadienes,
wherein
control
on
both
electrophile
part
is
achieved
for
first
time
photoinduced
butadienes.
This
delivers
structurally
novel
chiral
spiroindolenines
two
contiguous
stereogenic
centers
high
diastereomeric
ratios
(up
>20
:
1
dr)
good
excellent
enantiomeric
97
3
er).
Experimental
computational
studies
mechanism
confirmed
radical
pathway
involving
excited-state
palladium
catalysis.
The
alignment
non-covalent
interactions
between
substrate
catalyst
were
found
be
essential
stereocontrol.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9254 - 9264
Опубликована: Июнь 3, 2024
Catalytic
asymmetric
dearomatization
reactions
of
α-unsubstituted
β-naphthols
are
very
challenging
due
to
the
high
energy
barrier
resulting
from
loss
aromaticity.
Herein,
we
describe
an
example
enantioselective
catalytic
dearomative
spiroannulation
with
yne-allylic
esters.
The
success
this
reaction
relied
on
copper-catalyzed
remote
strategy
using
esters
as
bis-electrophilic
reagents.
This
transformation
features
mild
conditions,
broad
functional
group
tolerance,
and
extensive
substrate
scope,
thereby
facilitating
efficient
construction
array
enantioenriched
naphthalene-2-one
spiroindolenine
derivatives.
Experimental
studies
density
theory
calculations
establish
pathway
origin
stereoselectivity.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1088 - 1093
Опубликована: Янв. 25, 2024
Herein,
we
report
the
discovery
of
ipso-selective,
dearomatizing
spirocyclization
indole-tethered
epoxides
as
a
fundamentally
new
approach
for
constructing
spiroindolenines
equipped
with
three
contiguous
stereogenic
centers
under
complete
diastereocontrol
(dr
>99:1)
and
in
high
yields.
Promoted
by
hexafluoroisopropanol,
protocol
features
broad
substrate
scope,
easy
scale-up,
versatile
transformations
synthesized
spiroindolenines.
Tetrahedron Chem,
Год журнала:
2024,
Номер
9, С. 100055 - 100055
Опубликована: Янв. 14, 2024
This
review
concentrates
on
our
research
into
the
discovery
of
novel
ynone-based
dearomative
spirocyclisation
processes,
whilst
placing
new
chemistry
context
existing
knowledge.
The
genesis
programme,
development
efficient
synthetic
routes
to
prepare
natural
products
spirobacillene
A
(1)
and
B
(2),
utilised
indole
ynones.
stimulated
a
much
wider
study
explore
reactivity
ynones
in
processes
more
generally.
Routes
generate
wide
range
spirocycles
were
subsequently
developed,
with
reactions
tethered
indoles,
benzofurans,
benzisoxazoles,
pyrroles,
pyridines,
isoquinolines,
pyrazines,
cyclic
ketimines,
anisoles
all
discussed
herein,
these
initiated
by
catalytic
Ag(I),
Cu(II),
Pd(0),
photolysis
many
other
reagents.
Asymmetric
variants
some
are
also
discussed,
as
is
further
elaboration
spirocyclic
give
carbazoles,
quinolones,
polycycles
useful
building
blocks.
Finally,
applications
methodology
product
synthesis
(e.g.
A,
lasubine
II
indolizidine
209D)
described.
Journal of Heterocyclic Chemistry,
Год журнала:
2024,
Номер
61(3), С. 528 - 537
Опубликована: Янв. 16, 2024
Abstract
A
dearomative
[4
+
2]
cycloaddition
of
3‐nitroindoles
ortho
‐amino
Morita−Baylis−Hillman
carbonates
was
established
under
mild
conditions.
This
method
provides
an
efficient
and
practical
approach
for
delivering
tetrahydro‐5
H
‐indolo[2,3‐
b
]quinolines
containing
three
contiguous
stereocenters,
two
tertiary
one
quaternary,
in
high
yield
(up
to
95%)
with
excellent
diastereoselectivity
(all
cases
>25:1
dr
).
The
potential
synthetic
applications
this
strategy
were
also
highlighted
by
the
scale‐up
experiment
further
transformation.
Moreover,
structure
relative
configuration
cycloadduct
unequivocally
confirmed
single‐crystal
X‐ray
diffraction.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(5), С. 1044 - 1058
Опубликована: Янв. 12, 2024
Abstract
This
review
centers
on
the
synthetic
strategies
employed
with
indolyl‐ynones.
Indolyl‐ynone,
owing
to
its
highly
reactive
ynone
moiety,
frequently
partakes
in
dearomatizing
spirocyclization
reactions
and
subsequent
rearrangement
when
subjected
various
reaction
conditions.
Hence,
heterocycles
such
as
densely
functionalized
spiroindolenines,
carbazoles,
quinolines
carbo‐and
hetero‐cycle
substituted
indoles
are
synthesized
from
In
addition
this,
versatile
spirocyclic
indole
scaffold
exhibits
capability
produce
tetracyclic
polyclic
structures
through
intricate
skeletal
processes.
Moreover,
total
synthesis
of
natural
products
using
indolyl‐ynone
moiety
was
also
compiled
this
review.
Organic Letters,
Год журнала:
2023,
Номер
25(48), С. 8771 - 8776
Опубликована: Ноя. 28, 2023
A
catalyst-free
gem-difluorination/spirocyclization
reaction
has
been
successfully
developed
for
the
synthesis
of
gem-difluorinated
C2-spiroindoline
derivatives
from
indole-2-carboxamides.
The
resulting
C2-spiroindolines
can
be
easily
converted
into
2-spiropseudoindoxyls
through
hydrolysis.
This
method
offers
benefits
simple
operation,
convenient
access
to
raw
materials,
and
mild
conditions.
Dual
function
Selectfluor
in
this
is
noteworthy
as
it
serve
both
a
fluorinating
agent
an
alkaline
accelerator
precursor.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(7), С. 1933 - 1940
Опубликована: Янв. 1, 2024
A
new
one-pot
method
for
solvent-controlled
switchable
tandem
oxidative
triple
functionalization
of
indolines
has
been
developed
via
successive
regioselective
chalcogenation,
oxidation,
amination
and
halogenation.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Direct
functionalization
of
native
(N–H)
indoles
via
C–H
activation
remains
a
challenge.
Herein,
we
report
salicylaldehyde-promoted
cobalt-catalyzed
selective
C2–H
Heck
reaction
with
both
active
and
unactivated
olefins
in
the
presence
free
N–H
bonds.
A
series
structurally
diverse
C2-alkenylated
including
natural
product
drug
derivatives
were
prepared
directly
effectively
without
additional
preprotection
deprotection
procedures.