Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1615 - 1626
Опубликована: Фев. 7, 2024
Abstract
Herein,
we
describe
a
base‐promoted
regioselective
and
chemoselective
cascade
cyclization,
ynamide
N−C
sp
bond
cleavage,
selective
intramolecular
1,3‐migration,
simultaneous
N
‐desulfonylation
strategy
for
the
synthesis
of
2‐phenyl‐3‐(phenylethynyl)‐1H‐indole
derivatives.
We
observed
multiple
breaking
(−N−Ts,
C
2
−Ts,
−I/C
−SePh)
from
(
E
)‐3‐(1‐iodo‐2‐phenyl‐2‐tosylvinyl)‐2‐phenyl‐1‐tosyl‐indole/(
)‐2‐phenyl‐3‐(2‐phenyl‐1‐(phenylselanyl)‐2‐tosylvinyl)‐1‐tosyl‐indole
derivatives
to
prepare
in
15–60
min
using
our
standard
reaction
conditions.
A
gram‐scale
experiment
as
well
postsynthetic
transformations
synthesized
were
performed
exhibit
advantages
this
synthetic
methodology.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
58(2), С. 281 - 298
Опубликована: Янв. 3, 2025
ConspectusControlling
selectivity
through
manipulation
of
reaction
intermediates
remains
one
the
most
enduring
challenges
in
organic
chemistry,
providing
novel
solutions
for
selective
C-C
π-bond
functionalization.
This
approach,
guided
by
activation
principles,
provides
an
effective
method
functional
group
installation,
enabling
direct
synthesis
molecules
that
are
inaccessible
conventional
pathways.
In
particular,
functionalization
N-conjugated
allenes
and
alkynes
has
emerged
as
a
promising
research
focus,
driven
advances
controlling
reactive
strategies.
this
regard,
our
group,
alongside
others,
established
some
new
approaches
have
suitable
platform
functionalized
enamides.
Account
reviews
recent
developments
field,
highlighting
modes
reactivity
selectivity,
atom-economical
functionalizations,
strategies
regio-
stereocontrol,
while
mechanistic
insights
into
related
transformations.Our
study
is
systematically
organized
two
sections
based
on
substrate
type
chronological
progression.
first
section,
we
establish
allenamide-derived
intermediates,
both
allenamide-alkyne
(AA)
cross-coupling
few
electrophile-promoted
hydrofunctionalization
reactions.
The
unprecedented
Pd-catalyzed
achieved
neighboring
chelation,
with
phosphine
ligand
selection
outcome.
parallel,
functionalizations─including
haloalkynylation,
hydrooxycarbonylation,
hydrodifluoroalkylation,
intermolecular
hydroamination─are
strategic
electrophiles
or
their
precursors.Additionally,
findings
demonstrate
how
ynamides'
toward
nucleophiles,
controlled
activator
modulation,
expands
scope
accessible
transformations.
Key
include:
(1)
chemoselective
[2
+
2
2]
annulation
efficient
trapping
N-arylated
nitrilium
ynamides,
(2)
divergent
C-H
indole-derived
vinylogous
ynamides
metal
via
intramolecular
hydroarylation,
(3)
bromoalkynylation-enabled
migration
1,3-alkynyl
shift.The
final
section
explores
N-electron
polarization
1,3-enynes
enables
chemoselectivity
metal-free
inter-
couplings
indole
substrates.
Our
modulating
conjugation
within
enyne
skeleton─through
linear
cross
conjugation─can
pathways
control
product
selectivity.This
aims
to
stimulate
broader
intermediate-controlled
activated
π-systems.
Future
directions
include
advanced
design,
strategies,
deeper
studies
enable
rational
development.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7009 - 7013
Опубликована: Сен. 14, 2023
The
1,2-iminylalkylation
of
diazenes
using
alkyl
iodides
in
combination
with
an
O-benzoyl
oxime
is
reported.
In
this
transformation,
acted
as
a
radical
precursor
and
XAT
mediator.
addition
to
common
iodides,
other
such
iodomethane,
iodomethane-d3,
trifluoroiodomethane,
ethyl
difluoroiodoacetate,
iodoalkanes
containing
unprotected
hydroxyl
amide
groups
can
also
serve
C-radical
precursors
the
electrophilic
acceptors.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(8), С. 2351 - 2374
Опубликована: Янв. 1, 2024
This
review
carefully
summarizes
the
advances
achieved
in
catalytic
hydrofunctionalization
of
ynamides
and
is
categorized
by
bond
formation
type
including
C−C,
C−X,
C−O,
C−N,
C−S,
C−P,
C−Si,
C−Ge
bonds.
Organic Letters,
Год журнала:
2024,
Номер
26(17), С. 3503 - 3508
Опубликована: Апрель 25, 2024
A
metal-free
TMSOTf-catalyzed
[4
+
2]
annulation
of
ynamides
with
β-(2-aminophenyl)-α,β-ynones
enables
the
regiospecific
and
facile
assembly
2-aminoquinoline
frameworks.
The
catalyst
TMSOTf
presented
a
remarkable
advancement
compared
to
previously
reported
transition-metal
catalysts.
wide
range
3-aryl/alkyl-substituted
2-aminoquinolines
were
generated
in
moderate
excellent
yields
due
mild
conditions.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
Reported
herein
is
a
concise
synthesis
of
sulfoximidoyl
amidines
enabled
by
Pd-catalyzed
cascade
aza-Claisen
rearrangement
and
nucleophilic
reaction
at
room
temperature.
Free
NH-sulfoximines
N-allylynamides
were
employed
as
the
modular
building
blocks
to
produce
expected
sulfoximine
amidine
derivatives
in
highly
chemoselective
models
100%
atom
efficiency.
A
broad
range
functional
groups
well
tolerated
under
these
gentle
conditions
give
desired
products
generally
good
excellent
yields.
α-Fluoro-α′-aryl
ketones
are
crucial
in
pharmaceuticals
and
agrochemicals.
However,
synthesizing
unsymmetrical
α-fluoro-α′-aryl
poses
regioselective
challenges.
This
study
presents
a
one-pot
aryl-oxy-fluorination
method
for
such
fluoro-aryl
ketones.
Using
ynamide,
aryl
boronic
acid,
F-source
under
Pd-catalysis,
this
efficiently
produces
wide
range
of
valuable
with
potential
applications.
Through
combination
control
experiments
DFT
studies,
we
proposed
reaction
mechanism
involving
situ
acetic
acid
formation.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Herein,
we
report
an
HFIP-mediated,
versatile,
sustainable,
atom-economical,
and
regio-
stereoselective
hydro-functionalization
of
ynamides
with
various
S-nucleophiles
(1
equiv.)
such
as
thiols,
thiocarboxylic
acids,
carbamates,
xanthates,
O,O-diethyl
S-hydrogen
phosphorothioate
to
access
a
wide
variety
stereodefined
trisubstituted
ketene
N,S-acetals
under
mild
conditions.
This
protocol
requires
only
HFIP,
which
plays
multiple
roles,
acting
Brønsted
acid
protonate
the
ynamide
regioselectively
at
beta
carbon
generate
reactive
keteniminium
intermediate,
stabilizing
intermediate
solvent
through
H-bonding.
After
nucleophilic
attack
S-nucleophile
on
deprotonation,
HFIP
is
regenerated
in
most
cases
can
be
easily
recovered
recycled,
revealing
high
sustainability
protocol.
Remarkably,
all
reactions
are
highly
efficient
furnish
excellent
yields
many
pure
products
were
obtained
just
by
washing
crude
reaction
mixture
pentane.
Significantly,
green
chemistry
metrics
found
excellent.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 9, 2025
An
effective
strategy
to
synthesize
2,4-diaminoquinoline
compounds
has
been
efficaciously
developed
via
a
TMSOTf/TfOH-promoted
[4
+
2]
annulation
of
ynamides
with
2-aminoarylnitriles.
Compared
the
reported
transition-metal
catalysts,
this
metal-free
promotion
system
presented
remarkable
advancement,
enabling
facile
and
regiospecific
assembly
frameworks
wide
functional
group
compatibility
moderate
excellent
yields.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 22, 2025
Fluorine
and
nitrogen
form
a
successful
partnership
in
organic
synthesis,
medicinal
chemistry,
material
sciences.
Although
fluorine-nitrogen
chemistry
has
long
rich
history,
this
field
received
increasing
interest
made
remarkable
progress
over
the
past
two
decades,
driven
by
recent
advancements
transition
metal
organocatalysis
photochemistry.
This
review,
emphasizing
contributions
from
2015
to
2023,
aims
update
state
of
art
synthesis
applications
nitrogen-based
organofluorine
functional
molecules
chemistry.
In
dedicated
sections,
we
first
focus
on
fluorine-containing
reagents
organized
according
type
groups
attached
nitrogen,
including
N-F,
N-RF,
N-SRF,
N-ORF.
review
also
covers
nitrogen-linked
building
blocks,
catalysts,
pharmaceuticals,
agrochemicals,
underlining
these
components'
broad
applicability
growing
importance
modern
