Angewandte Chemie,
Год журнала:
2024,
Номер
136(12)
Опубликована: Янв. 26, 2024
Abstract
In
this
report,
we
describe
the
use
of
amino‐λ
3
‐iodanes
in
electrophilic
amination
arylboronic
acids
and
boronates.
Iodine(III)
reagents
with
transferable
amino
groups,
including
one
an
NH
2
group,
were
synthesized
used
amination,
allowing
synthesis
a
wide
range
primary
secondary
(hetero)arylamines.
Mechanistic
studies
by
DFT
calculations
indicate
that
reaction
proceeds
through
process
from
tetravalent
borate
complex
B−N
dative
bond.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
145(1), С. 41 - 46
Опубликована: Дек. 23, 2022
A
synthetic
method
for
the
reductive
transformation
of
nitroarenes
into
ortho-aminated
and
-annulated
products
is
reported.
The
operates
via
exhaustive
deoxygenation
by
an
organophosphorus
catalyst
a
mild
terminal
reductant
to
access
aryl
nitrenes,
which
after
ring
expansion,
are
trapped
amine
nucleophiles
give
dearomatized
2-amino-3H-azepines.
Treatment
these
ring-expanded
intermediates
with
acyl
electrophiles
triggers
6π
electrocyclization
extrude
nitrogen
atom
restore
aromaticity
phenyl
ring,
delivers
C–H
functionalization
2-aminoanilide
benzimidazole
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(12)
Опубликована: Янв. 26, 2024
Abstract
In
this
report,
we
describe
the
use
of
amino‐λ
3
‐iodanes
in
electrophilic
amination
arylboronic
acids
and
boronates.
Iodine(III)
reagents
with
transferable
amino
groups,
including
one
an
NH
2
group,
were
synthesized
used
amination,
allowing
synthesis
a
wide
range
primary
secondary
(hetero)arylamines.
Mechanistic
studies
by
DFT
calculations
indicate
that
reaction
proceeds
through
process
from
tetravalent
borate
complex
B−N
dative
bond.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 14136 - 14148
Опубликована: Апрель 20, 2024
An
unprecedented
chiral
bisphosphine-catalyzed
asymmetric
Staudinger/aza-Wittig
reaction
of
2,2-disubstituted
cyclohexane-1,3-diones
is
reported,
enabling
the
facile
access
a
broad
range
cis-3a-arylhydroindoles
in
high
yields
with
excellent
enantioselectivities.
The
key
to
success
this
work
relies
on
first
application
bisphosphine
DuanPhos
reaction.
effective
reductive
system
has
been
established
address
challenging
PV═O/PIII
redox
cycle
associated
catalyst.
In
addition,
comprehensive
experimental
and
computational
investigations
were
carried
out
elucidate
mechanism
Leveraging
newly
developed
chemistry,
enantioselective
total
syntheses
several
crinine-type
Amaryllidaceae
alkaloids,
including
(+)-powelline,
(+)-buphanamine,
(+)-vittatine,
(+)-crinane,
have
accomplished
remarkable
conciseness
efficiency.
Chemical Communications,
Год журнала:
2024,
Номер
60(67), С. 8806 - 8823
Опубликована: Янв. 1, 2024
Distinct
reactivity
and
chemoselectives
of
photoexcited
nitroarenes
under
visible
light
irradiation
such
as
reductive
C–N
coupling,
anaerobic
oxidation,
annulation,
scaffold
diversification
via
nitrene
insertion,
etc.
,
are
highlighted.
Organic Letters,
Год журнала:
2023,
Номер
25(49), С. 8872 - 8876
Опубликована: Дек. 4, 2023
An
efficient
photocatalytic
C–N
cross-coupling
of
nitroarenes
with
haloarenes
has
been
developed
using
simple
and
cheap
Ni(acac)2
as
a
cocatalyst.
The
reaction
is
confirmed
stepwise
process:
(1)
metal
free
photoinduced
reduction
into
aniline
derivatives
(2)
photo-
Ni-catalyzed
anilines
haloarenes.
conditions
are
mild,
giving
high-value
diarylamines
good
to
excellent
yields
functional
group
tolerance.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(2), С. 1083 - 1090
Опубликована: Янв. 4, 2024
A
metal-free
and
thiol-free
organophosphorus-catalyzed
method
for
forming
thioethers
was
disclosed,
driven
by
PIII/PV═O
redox
cycling.
In
this
work,
one-step
dehydroxylative
thioetherification
of
alcohols
fulfilled
with
various
hypervalent
organosulfur
compounds.
This
established
strategy
features
an
excellent
functional
group
tolerance
broad
substrate
scope,
especially
inactivated
alcohols.
The
scale-up
reaction
further
transformation
the
product
were
also
successful.
Additionally,
offers
a
protecting-group-free
step-efficient
approach
synthesizing
peroxisome
proliferator-activated
receptor
agonists
which
exhibited
promising
potential
treating
osteoporosis
in
mammals.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7848 - 7858
Опубликована: Май 29, 2024
A
CuH-catalyzed
reductive
coupling
of
nitroarenes
with
phosphine
oxides
is
developed,
which
produces
a
series
phosphamides
in
moderate
to
excellent
yields
good
functional
group
tolerance.
Gram-scale
synthesis
and
late-stage
modification
nitro-aromatic
molecule
niclosamide
are
also
successfully
conducted.
The
mechanism
study
shows
that
the
nitro
transformed
after
being
reduced
nitroso
nucleophilic
addition
procedure
involved
during
reaction.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(14)
Опубликована: Дек. 27, 2022
The
syntheses
of
the
first
B9-connected
carboranylphosphines
(B9-Phos)
featuring
two
carboranyl
moieties
as
well
access
to
B9-Phos
ligands
with
bulky
electron-donating
substituents,
previously
deemed
unattainable,
is
reported.
electrochemical
properties
were
investigated,
revealing
ability
mesityl
derivatives
form
stabilized
phosphoniumyl
radical
cations.
display
an
extremely
electron-releasing
character
surpassing
that
alkyl
phosphines
and
commonly
used
N-heterocyclic
carbenes.
This
demonstrated
by
their
very
small
Tolman
electronic
parameters
(TEPs)
low
P-Se
coupling
constants.
Cone
angles
buried
volumes
attest
high
steric
demand
exerted
(di)carboranyl
phosphines.
dicarboranyl
phosphine
AuI
complexes
show
superior
catalytic
performance
in
hydroamination
alkynes
compared
monocarboranyl
analogs.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Сен. 28, 2023
Organobismuth-catalyzed
transfer
hydrogenation
has
recently
been
disclosed
as
an
example
of
low-valent
Bi
redox
catalysis.
However,
its
mechanistic
details
have
remained
speculative.
Herein,
we
report
experimental
and
computational
studies
that
provide
insights
into
a
Bi-catalyzed
azoarenes
using
p-trifluoromethylphenol
(4)
pinacolborane
(5)
hydrogen
sources.
A
kinetic
analysis
elucidated
the
rate
orders
in
all
components
catalytic
reaction
determined
1
(2,6-bis[N-(tert-butyl)iminomethyl]phenylbismuth)
is
resting
state.
In
azobenzene
4,
equilibrium
between
⋅
[OAr]2
(Ar=p-CF3
-C6
H4
)
observed,
thermodynamic
parameters
are
established
through
variable-temperature
NMR
studies.
Additionally,
pKa
-gated
reactivity
validating
proton-coupled
nature
transformation.
The
ensuing
crystallographically
characterized,
shown
to
be
rapidly
reduced
presence
5.
DFT
calculations
indicate
rate-limiting
transition
state
which
initial
N-H
bond
formed
via
concerted
proton
upon
nucleophilic
addition
hydrogen-bonded
adduct
4.
These
guided
discovery
second-generation
catalyst,
lower
energy,
leading
at
catalyst
loadings
cryogenic
temperature.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
The
ongoing
discovery
of
highly
reactive
ambiphilic
main-group
species
has
significantly
advanced
the
development
chemistry,
particularly
in
realms
small
molecule
activation
and
catalysis.
Theoretically,
compounds
featuring
smaller
HOMO–LUMO
gaps
gain
stronger
ambiphilicity
higher
reactivity.
In
this
work,
we
fundamentally
demonstrate
that
Me3Sb
holds
smallest
gap
among
trimethylpnictines,
indicating
its
outstanding
ambiphilicity.
Correspondingly,
superior
reactivity
toward
deoxygenation
electron-deficient
nitroarenes
been
unambiguously
revealed
through
control
experiments.
Furthermore,
unprecedented
SbIII/SbVO
cycling
between
trialkylstibines
their
oxides
established
for
catalytic
transformation
into
azoxyarenes/azoarenes.
This
study
opens
a
new
chapter
organoantimony
derivatives
fields
redox
