Royal Society of Chemistry eBooks,
Journal Year:
2024,
Volume and Issue:
unknown, P. 93 - 116
Published: Dec. 6, 2024
Within
the
last
two
decades
iron-catalysis
has
gained
considerable
traction
in
field
of
hydroboration.
Use
iron
is
an
attractive
strategy
towards
more
earth-abundant
transition
metal
catalysis.
Its
ability
to
occupy
a
variety
different
oxidation
states
can
unlock
world
unique
reactivities
and
enable
comparable
reaction
profiles
its
precious
counterparts.
Hydroboration
widely
regarded
as
important
transformation
for
assessing
catalytic
reactivity
newly
designed
catalyst
systems.
In
this
chapter,
we
will
review
current
literature
iron-catalysed
hydroboration
reactions
range
unsaturated
C–C
C–heteroatom
bonds.
Dalton Transactions,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
Fe
II
complex
[FeCp*{N(SiMe
3
)
2
}]
reacts
readily
with
formamidinium
cations
(
i.e.
protonated
NHCs)
in
the
presence
of
halide
anions
via
[FeCp*X{N(SiMe
−
(X
=
Cl,
Br,
I)
to
furnish
[FeCp*X(NHC)]
and
HN(SiMe
,
but
is
inert
towards
NHC-H[BF
4
].
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 28, 2025
We
report
a
well-defined
multifunctional
iron
catalyst,
Cp*Fe(Ph2PN
=
C5H4N),
that
promotes
the
rearrangement
of
β,γ-unsaturated
ketones,
esters,
and
amides
to
their
α,β-isomers,
enabling
regioselective
C═C
reductive
deuteration.
This
iron-catalyzed
protocol
showcases
synthesis
diverse
range
α,β-dideuterated
organic
compounds,
demonstrating
broad
substrate
compatibility
under
mild
conditions.
Mechanism
studies
provide
insights
into
bond
relocation
cooperative
D2
activation.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(37), P. 15023 - 15086
Published: Jan. 1, 2024
The
expansive
and
dynamic
field
of
the
CO2
Reduction
Reaction
(CO2RR)
seeks
to
harness
as
a
sustainable
carbon
source
or
energy
carrier.
While
significant
progress
has
been
made
in
two,
six,
eight-electron
reductions
CO2,
four-electron
reduction
remains
understudied.
This
review
fills
this
gap,
comprehensively
exploring
into
formaldehyde
(HCHO)
acetal-type
compounds
(EOCH2OE,
with
E
=
[Si],
[B],
[Zr],
[U],
[Y],
[Nb],
[Ta]
-R)
using
various
CO2RR
systems.
These
encompass
(photo)electro-,
bio-,
thermal
processes
diverse
reductants.
Formaldehyde,
versatile
C1
product,
is
challenging
synthesize
isolate
from
CO2RR.
also
discusses
acetal
compounds,
emphasizing
their
significance
pathways
distinct
reactivity.
Providing
an
overview
state
reduction,
highlights
achievements,
challenges,
potential
produced
-
acetals
sources
for
valuable
product
synthesis,
including
chiral
compounds.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
26(1), P. 439 - 447
Published: Nov. 23, 2023
The
selective
N
-formylation
and
-methylation
of
amines
with
carbon
dioxide
(CO
2
)
catalyzed
by
methyltriphenylphosphonium
methylcarbonate
tuned
polymethylhydrosiloxane
or
trimethoxysilane
as
reducing
agents
is
reported.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(18), P. 8244 - 8256
Published: April 24, 2024
The
borane-functionalized
(BR2)
bis(3,5-dimethylpyrazolyl)methane
(LH)
ligands
1a
(BR2:
9-borabicyclo[3.3.1]nonane
or
9-BBN),
1b
BCy2),
and
1c
B(C6F5)2)
were
synthesized
by
the
allylation–hydroboration
of
LH.
Metalation
1a,b
with
ZnCl2
yielded
heteroscorpionate
dichloride
complexes
[(1a,b)ZnCl2]
3a,b.
reaction
ZnEt2
led
to
formation
zwitterionic
complex
[Et(1a)ZnEt(THF)]
5.
3a
two
equivalents
KHBEt3
under
a
carbon
dioxide
(CO2)
atmosphere
gave
rise
dimeric
bis(formate)
[(1a)Zn(OCHO)2]2
8,
in
which
its
borane
moieties
intermolecularly
stabilize
formate
opposite
metal
centers.
allylated
precursor
Lallyl
zinc
dichloride,
diethyl
[(Lallyl)ZnCl2]
2,
[(Lallyl)ZnEt2]
4,
[(Lallyl)Zn(OCHO)2]
7
also
isolated.
catalyst
systems
composed
1
mol
%
3b
hydroborated
CO2
at
bar
pinacolborane
(HBPin)
methanol-level
product
H3COBPin
(and
PinBOBPin)
yields
42
86%,
respectively.
using
unfunctionalized
[(LH)ZnCl2]
6
KHBEt3/nOctBR2
9-BBN
BCy2)
but
2.5-
6-fold
lower
activities
than
those
exhibited
3a,b/KHBEt3.
hydroboration
8
as
39–43%,
comparable
obtained
3a/KHBEt3.
results
confirmed
that
catalytic
intermediates
benefit
from
incorporated
boranes'
intra-
intermolecular
stabilizations.
ChemSusChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: June 14, 2024
Abstract
Diphenylformamide
1
and
bisformamide
9
are
shown
to
be
safe
reservoirs
sources
of
CO.
Their
perfectly
selective
decarbonylations
achieved
in
solution
at
room
temperature
with
potassium
cesium
diarylamide
catalysts.
is
obtained
excellent
yields
directly
from
triethylammonium
formate,
which
may
the
product
CO
2
scrubbing
NEt
3
catalytic
hydrogenation.
thus
represents
a
key
intermediate
low‐temperature
rWGS
reaction
sequence.
Moreover,
solvent‐free
run
either
melt
70
°C
or
even
solid
state
88
improved
atom
economy.
These
simple
practical
transition‐metal‐free
afford
ultra‐pure
(
i.
e
.
dry
solvent‐free)
moderate
temperatures
diarylamines
byproducts
recycled
as
pure
compounds.
In
absence
catalysts,
diarylformamides
long‐term
stable
>200
°C.
DFT‐calculations
indicate
pathway
rate‐determining
deprotonation
Ph
NC(O)H
barrier‐free
elimination
NC(O)
−
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(9), P. 6149 - 6158
Published: April 18, 2024
The
detailed
mechanism
of
transition
metal-free-catalyzed
monomethylation
2-naphthyl
acetonitrile
(1a)
with
CO2
in
the
presence
triazabicyclodecene
(TBD)
and
BH3NMe3
was
investigated
using
density
functional
theory.
C-methylation
process
proved
to
generate
formaldehyde
followed
by
formation
product
via
an
alcohol
rather
than
a
methoxyborane
intermediate.
During
reaction,
is
activated
form
TBD-CO2
adduct
changed
into
TBD-BH2
(IM2)
TBD.
IM2
plays
real
reducing
role
within
system
due
unique
coordination
capability
B
atom.
In
addition
enhancing
nucleophilicity
1a
through
deprotonation
tBuOK,
our
research
also
indicates
that
generated
tBuOH
not
only
assists
proton
transfer
intermediate
but
promotes
regeneration
