Polyhedron,
Год журнала:
2024,
Номер
251, С. 116853 - 116853
Опубликована: Янв. 23, 2024
Iridium
dibromide
complexes
of
the
phenyldiimine
ligand
2,6-bis(1-((2,6-dimethylphenyl)imino)ethyl)phenyl,
trans-(XyPhDI)IrBr2L,
have
been
synthesized,
and
relative
Ir-L
BDFEs
experimentally
determined
for
a
wide
range
corresponding
adducts
ligands
L.
An
estimate
absolute
enthalpy
binding
has
obtained
from
dynamic
NMR
measurements.
The
results
DFT
calculations
are
in
very
good
agreement
with
experimental
values.
Computational
studies
were
extended
to
formation
(XyPhDI)IrH2
(XyPhDI)IrI,
as
well
other
(pincer)IrI
fragments,
(Phebox)IrI
(PCP)IrI,
enable
comparison
electronic
steric
effects
these
archetypal
pincer
ligands.
Attempts
reduce
(XyPhDI)IrBr2(MeCN)
hydride
or
an
IrI
complex
yielded
dinuclear
CN-bridged
methyl
on
cyanide-C-bound
Ir
center
(characterized
by
scXRD),
indicating
that
C-CN
bond
cleavage
took
place
at
center.
indicate
occurs
one
strong
assistance
coordination
CN
nitrogen
Chemical Reviews,
Год журнала:
2023,
Номер
123(19), С. 11269 - 11335
Опубликована: Сен. 26, 2023
Late-stage
functionalization
(LSF)
constitutes
a
powerful
strategy
for
the
assembly
or
diversification
of
novel
molecular
entities
with
improved
physicochemical
biological
activities.
LSF
can
thus
greatly
accelerate
development
medicinally
relevant
compounds,
crop
protecting
agents,
and
functional
materials.
Electrochemical
synthesis
has
emerged
as
an
environmentally
friendly
platform
transformation
organic
compounds.
Over
past
decade,
electrochemical
late-stage
(eLSF)
gained
major
momentum,
which
is
summarized
herein
up
to
February
2023.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 3427 - 3437
Опубликована: Янв. 20, 2024
Despite
half
a
century's
advance
in
the
field
of
transition-metal-catalyzed
asymmetric
alkene
hydrogenation,
enantioselective
hydrogenation
purely
alkyl-substituted
1,1-dialkylethenes
has
remained
an
unmet
challenge.
Herein,
we
describe
chiral
PCNOx-pincer
iridium
complex
for
transfer
this
class
with
ethanol,
furnishing
all-alkyl-substituted
tertiary
stereocenters.
High
levels
enantioselectivity
can
be
achieved
reactions
substrates
secondary/primary
and
primary/primary
alkyl
combinations.
The
catalyst
is
further
applied
to
redox
isomerization
disubstituted
alkenols,
producing
stereocenter
remote
resulting
carbonyl
group.
Mechanistic
studies
reveal
dihydride
species,
(PCNOx)Ir(H)2,
as
catalytically
active
intermediate,
which
decay
dimeric
species
(κ3-PCNOx)IrH(μ-H)2IrH(κ2-PCNOx)
via
ligand-remetalation
pathway.
deactivation
under
conditions
H2
much
faster
than
that
EtOH,
explains
why
(PCNOx)Ir
effective
but
ineffective
hydrogenation.
suppression
di-to-trisubstituted
by
regioselective
1,2-insertion
partly
responsible
success
system,
underscoring
critical
role
played
pincer
ligand
1,1-dialkylethenes.
Moreover,
computational
elucidate
significant
influence
London
dispersion
interaction
between
substrate
on
control,
illustrated
complete
reversal
stereochemistry
through
cyclohexyl-to-cyclopropyl
group
substitution
substrates.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5250 - 5265
Опубликована: Март 30, 2024
The
synthesis,
characterization,
and
catalytic
application
of
a
new
phosphine-free,
well-defined,
water-soluble,
air-stable
Mn(II)-catalyst
[Mn(L)(H2O)2Cl](Cl)
([1]Cl)
featuring
1,10-phenanthroline
based
tridentate
pincer
ligand,
2-(1H-pyrazol-1-yl)-1,10-phenanthroline
(L),
in
dehydrogenative
functionalization
alcohols
to
various
N-heterocycles
such
as
quinazolin-4(3H)-ones,
quinolines,
quinoxalines
are
reported
here.
A
wide
array
multisubstituted
quinazolin-4(3H)-ones
were
prepared
water
under
air
following
two
pathways
via
the
coupling
with
2-aminobenzamides
2-aminobenzonitriles,
respectively.
2-Aminobenzyl
alcohol
ketones
bearing
active
methylene
group
used
partners
for
synthesizing
quinoline
derivatives,
quinoxaline
derivatives
by
vicinal
diols
1,2-diamines.
In
all
cases,
reaction
proceeded
smoothly
using
our
[1]Cl
air,
affording
desired
satisfactory
yields
starting
from
cheap
readily
accessible
precursors.
Gram-scale
synthesis
compounds
indicates
industrial
relevance
synthetic
strategy.
Control
experiments
performed
understand
unveil
plausible
mechanism.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13536 - 13545
Опубликована: Май 2, 2024
Herein,
we
establish
a
remote
hydrosulfonamidation
(HSA)
of
alkenes
using
palladium
catalysis,
where
N-fluoro-N-(fluoro-sulfonyl)-carbamate
with
sulfur(VI)
fluoride
moiety
is
demonstrated
as
good
amidation
reagent.
The
anti-Markovnikov
HSA
reaction
terminal
and
the
internal
are
achieved
to
efficiently
yield
primary
N-alkyl-N-(fluorosulfonyl)-carbamates.
In
addition,
this
protocol
enables
high-value
utilization
alkane
by
combining
dehydrogenation
process.
generated
N-alkyl
products
exhibit
unique
reactivity
fluorides,
which
can
be
directly
transferred
sulfamides
or
amines
via
exchange
reaction,
thereby
streamlining
their
synthesis.
Moreover,
(pyridyl)
benzazole-type
ligand
proved
vital
for
excellent
chemo-
regioselectivities.
Abstract
In
the
last
two
decades,
pincer
metal
complexes
have
been
highly
utilized
as
catalysts
for
a
variety
of
organic
transformations
in
both
industrial
and
social
applications.
Owing
to
extraordinary
chemical
characteristics,
such
extra
thermal
stability
easy
functionalization,
they
were
extensively
generating
novel
catalytic
species.
Besides,
activity
these
was
achieved
with
high
atom
economy
eco‐friendly
routes.
Recently,
exhibited
excellent
behaviour
towards
various
immerging
systems,
hydrogenation
CO
2
,
nitriles,
amides,
esters,
olefins
alkynes,
which
are
valuable
production,
academic
research,
green
environment.
The
main
goal
this
reviewwas
highlight
how
function
reactions,
well
their
mechanistic
studies.
Specifically,
we
focus
on
most
updated
advancements
few
years.
Some
outlooks
future
suggestions
further
related
work
conclude
paper.
