Royal Society of Chemistry eBooks,
Journal Year:
2024,
Volume and Issue:
unknown, P. 117 - 149
Published: Dec. 6, 2024
This
chapter
provides
a
comprehensive
overview
of
recent
advancements
in
Mn(i)-catalysed
hydrogenation
and
dehydrogenation
reactions,
with
focus
on
their
application
hydrogen
storage
systems.
It
explores
the
reactivity
Mn(i)
complexes
formate
analogues,
as
well
catalytic
mechanisms,
highlighting
potential
these
catalysts
to
contribute
circular
carbon
economy.
The
investigates
use
carbonate
hydroxide
salts
amines
environmentally
friendly
materials
for
storage,
demonstrating
substantial
efficiency
high
evolution
yield
excellent
reloading
purity.
systems’
operation
below
100
°C
suggests
possibility
waste
heat
management
integration
into
process.
also
discusses
challenges
limitations
encountered,
such
decreased
subsequent
cycles
solubility
issues
certain
CO2
absorbents.
Overall,
presents
promising
candidates
renewable
energy
applications,
offering
insights
current
future
perspectives
development
efficient,
affordable,
sustainable
technologies.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(21), P. 4486 - 4491
Published: May 21, 2024
The
search
for
efficient
molecular
hydrogen
precursors
and
their
catalytic
exploration
is
necessary
the
evolution
of
transfer
hydrogenation.
Methyl
formate
(MF)
having
high
content
still
remains
unexplored
such
transformations.
Herein,
we
disclosed
a
bifunctional
Ir(III)-complex
catalyzed
chemoselective
TH
protocol
N-heteroarenes
azoarenes
using
MF.
A
variety
substrates
including
ten
bioactive
molecules
have
been
synthesized
under
mild
reaction
conditions.
probable
mechanistic
pathway
was
proposed
based
on
control
experiments
studies.
Molecules,
Journal Year:
2024,
Volume and Issue:
29(11), P. 2565 - 2565
Published: May 30, 2024
N-aryl-substituted
pyrrolidines
are
important
moieties
widely
found
in
bioactive
substances
and
drugs.
Herein,
we
present
a
practical
reductive
amination
of
diketones
with
anilines
for
the
synthesis
good
to
excellent
yields.
In
this
process,
were
furnished
via
successive
iridium-catalyzed
transfer
hydrogenation.
The
scale-up
performance,
water
as
solvent,
simple
operation,
well
derivation
drug
molecules
showcased
potential
application
organic
synthesis.
New Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
48(41), P. 17700 - 17705
Published: Jan. 1, 2024
A
practical
and
efficient
platform
for
the
synthesis
of
3,4-dihydroquinolones
through
successive
hydrolysis
transfer
hydrogenation
was
presented.
wide
range
2-chloroquinolines
were
compatible
with
this
catalytic
system
in
excellent
yields.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 17556 - 17570
Published: Nov. 14, 2024
The
mechanism
of
the
quinoline
transfer
hydrogenation
(TH)
by
aqueous
HCOOH
under
action
[Cp*Co(quinNH2)I]+
(A*;
quinNH2
=
8-aminoquinoline)
has
been
investigated
a
combination
experiments
and
density
functional
theory
(DFT)
calculations.
Variable-temperature
(−40
to
20
°C)
1H
NMR
in
absence
substrate
shows
rapid
equilibration
between
A*
formate
complex
[Cp*Co(quinNH2)(O2CH)]+
(B*)
upon
addition
HCOOH/NEt3
MeOH,
yielding
ΔH°
1.49
±
0.03
kcal
mol–1
ΔS°
1.92
0.06
cal
K–1.
This
equilibrium
mixture
slowly
converts
decarboxylation
deprotonation
paramagnetic
(S
1)
[Cp*Cp(quinNH2)]
(C*),
indirectly
identified
derivatization
[Cp*Co(CNtBu)2]
further
I2
oxidation
[Cp*Co(CNtBu)2I](I3).
rate
law
[Cp*Co(quinNH2)I]+-catalyzed
8-methylquinoline
(8MQ)
TH
with
D2O
at
80
°C
order
one
for
catalyst
zero
HCOOH,
constant
k
(1.52
0.05)
×
10–2
s–1
L.
(Q)
(k
(2.04
L)
selectively
yields
tetrahydroquinoline
doubly
D-labeled
C3
position
([3,3-D2]-THQ).
Under
same
conditions,
DCOOD
[2,3,3,4-D4]-THQ
(6.6
0.6)
10–3
L
(KIE
kH/kD
3.1
0.5),
while
H2O
[2,4-D2]-THQ.
DFT
calculations
Cp
model
system
point
catalytic
cycle
both
diamagnetic
intermediates.
A
key
aspect
is
that
H
atom
as
hydride
metal
center,
converting
[CpCo(quinNH2)(O2CH)]+
(B)
[CpCo(quinNH2)H]+
(D),
faster
than
its
proton
yield
[CpCp(quinNH2)]
(C).
variance
closely
related
8-hydroxyquinoline
ligand
(ACS
Catal.
2021,
11,
11906–11920),
underlining
decisive
roles
reaction
medium
selection
dehydrogenation
pathway.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(21), P. 8887 - 8892
Published: Jan. 1, 2024
A
cyclometalated
iridium(III)
complex
bearing
a
self-immolative
quinolinium
moiety
was
developed
as
ratiometric
substrate
for
transfer
hydrogenation
studies.
This
photoluminescent
probe
allowed
the
rapid
screening
of
variety
Ir
catalysts
using
microplate
reader,
offering
convenient
method
to
assess
activity
minimum
amount
catalyst
sample.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
The
efficient
preparation
of
long-chain
amines
via
a
one-step
transfer-hydrogenation/reductive-amination
reaction
(THRA)
polyenals
using
non-noble
ruthenium
catalyst
with
formate
and
isopropanol
as
hydrogen
sources
has
been
achieved.
Abstract
The
asymmetric
transfer
hydrogenation
of
various
dibenzo‐fused
azepines
including
5
H
‐dibenzo[
b
,
e
][1,4]diazepines,
dibenzo[
f
][1,4]thiazepines
and
11
]azepines
using
chiral
iridium
diamine
catalysts
HCO
2
H/NEt
3
as
the
hydrogen
source
has
been
accomplished.
A
range
10,11‐dihydro‐
5H
10,11‐dihydrodibenzo[
][1,4]thiazepine
6,11‐dihydro‐5
have
prepared
in
82–94%
yields
with
82–99%
ee.
Diversely
substituted
substrates
are
suitable
for
this
transformation,
a
number
functional
groups
tolerated.
Enantiocontrol
is
achieved
via
judicious
choice
catalyst,
additive
source.
synthetic
potential
reaction
explored
through
gram‐scale
reactions
without
loss
reactivity
optical
purity
further
transformations
on
products.
RSC Advances,
Journal Year:
2024,
Volume and Issue:
14(51), P. 38105 - 38109
Published: Jan. 1, 2024
A
mild
protocol
for
the
construction
of
β-and
γ-amino
alcohols
via
an
iridium-catalyzes
reductive
amination
and
transfer
hydrogenation
diketones
with
aromatic
amines
is
described.
RSC Advances,
Journal Year:
2024,
Volume and Issue:
14(51), P. 38146 - 38152
Published: Jan. 1, 2024
A
novel
reductive
sulfonamidation
of
alkynes
with
primary
and
secondary
sulfonamides
using
Cp*Ir
catalyst,
which
provides
inspiration
for
the
synthesis
diversified
in
good
efficiency
mild
reaction
conditions.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 24, 2024
Herein,
we
report
a
sustainable
and
efficient
method
for
the
synthesis
of
structurally
diverse
phthalimidines
from
2-formylbenzoic
acid
primary
amines
using
an
iridium-catalyzed
reductive
lactamization
strategy.
The
advantages
this
method,
such
as
use
water–ethanol
solvent,
broad
substrate
scope,
high
catalyst
efficiency
(S/C
up
to
10000),
good
scalability,
easy
purification,
enable
it
be
practical
approach
phthalimidines.
It
is
suggested
that
iridium
hydride
formation
involved
in
rate-limiting
step.
Synthetic
applications
late-stage
functionalization
medicinally
relevant
molecules
are
also
demonstrated.
