The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 20, 2024
Six
fundamental
chemical
transformations
of
aryl
carbonyls
are
achieved
by
properly
adjusting
the
stoichiometry
borane-amine
and
titanium
tetrachloride
reagent
system.
This
set
reagents
acts
collectively
as
a
hydride
donor,
Lewis
acid
catalyst,
halogen
source
for
reduction
to
alcohols,
reductive
halogenation
halides,
deoxygenation
alkanes,
dehydroxyhalogenation
alcohols
hydrodehalogenation
halides
alkanes.
While
carbonyl
is
broadly
applicable
both
aromatic
aliphatic
substrates,
remaining
reactions
dependent
on
stability
proposed
carbocationic
intermediates,
enabling
highly
selective
at
substrates'
benzylic
position.
unique
selectivity
allows
dehalogenation
in
presence
alkyl
addition
even
tertiary
versus
secondary
primary
substrates
using
only
chlorinating
agent.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(33), P. 6650 - 6664
Published: Jan. 1, 2024
Titanium,
as
an
important
transition
metal,
has
garnered
extensive
attention
in
both
industry
and
academia
due
to
its
excellent
mechanical
properties,
corrosion
resistance,
unique
reactivity
organic
synthesis.
In
the
field
of
photocatalysis,
titanium-based
compounds
such
titanium
dioxide
(TiO
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Borenium
ions
have
attracted
significant
attention
in
organic
transformations
due
to
their
strong
Lewis
acidity.
The
reported
borenium
are
often
stabilized
by
sterically
demanding
substituents
and
coordination
bonds.
Herein,
we
synthesized
a
small
steric
borenium-equivalent
NH3BH2OTf
subjected
it
the
exhaustive
reduction
of
carboxylic
functional
group
methyl
group,
which
shows
broad
tolerance.
This
system
can
also
undergo
reductive
deoxygenation
reaction
alcohols,
ethers,
other
oxo-chemicals
(>100
examples).
mechanistic
studies
revealed
that
situ-generated
NH3BH2OTf/[NH3BH2(sol)]OTf,
rendering
borenium-like
properties,
plays
crucial
role
these
interacting
with
O
atom
substrates
activate
carbonyl
facilitating
cleavage
C–O
bond.
work
has
not
only
offered
for
but
is
great
significance
providing
insight
into
application
various
reactions.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
titanium-catalyzed
reductive
cyclization
of
vinyl
boronates
with
gem
-dihaloalkanes
is
developed.
α-Substituted
cyclic
that
are
otherwise
difficult
to
access,
such
as
those
heteroatom-containing
rings,
readily
obtained.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 4249 - 4264
Published: March 5, 2024
The
development
of
simple
and
general
catalytic
methods
using
abundant
base
metal
catalysts
for
the
deoxygenation
organic
compounds
valorization
biomass
chemical
synthesis
remains
a
formidable
challenge.
Cobalt
pincer-catalyzed
reductive
aldehydes,
ketones,
alcohols,
ethers
to
their
corresponding
alkanes
is
reported.
Biomass-derived
were
deoxygenated
methylarenes.
This
system
employs
diethylsilane
as
reductant
requires
substoichiometric
amount
base.
Investigations
revealed
initial
deprotonation
amine
arm
on
catalyst,
catalysis
begins
with
Si–H
activation
silane
facilitated
by
amine-amide
metal–ligand
cooperation.
In
situ-formed
Co–H
species
carry
out
hydrosilylation
carbonyl
compounds,
dehydrosilylation
hydrosilanolysis
ethers,
resulting
in
common
arylmethylsilyl
or
alkylsilyl
ether
intermediates.
Further,
reaction
leads
formation
siloxane
oligomers.
DFT
study
reveals
closely
lying
singlet–triplet
electronic
states
different
intermediates
facilitating
mechanism
spin
surfaces,
verified
through
located
minimum
energy
crossing
points
(MECPs).
case
alcohol,
another
low
pathway
where
amide
pincer,
instead
hydride,
can
abstract
hydroxy
proton
enable
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(5), P. 932 - 939
Published: Jan. 1, 2024
A
rapid
and
mild
protocol
for
the
exhaustive
deoxygenation
of
various
aromatic
ketones
to
corresponding
alkanes
using
AB
as
a
reductant
TiCl
4
catalyst.
Organometallics,
Journal Year:
2023,
Volume and Issue:
42(12), P. 1248 - 1253
Published: March 2, 2023
Hydrodehalogenation
is
a
straightforward
approach
to
detoxifying
harmful
organohalides,
in
which
the
halogen
atom
formally
substituted
with
hydrogen
atom.
Herein,
catalytic
system
using
Cp2TiCl2
as
catalyst
and
ammonia–borane
reductant
described.
A
series
of
benzyl
halides
inactivated
alkyl
(including
chlorides)
readily
reacted
give
corresponding
hydrodehalogenated
products
yields
up
97%
(43
examples).
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
reduction
of
aryl
carboxylates
to
methyl
and
allyl
arene
was
attained
using
a
well-defined
cobalt
catalyst.
This
catalytic
transformation
employs
only
sub-stoichiometric
amount
base,
diethylsilane
as
reductant.
Catalytic
activation
the
Si-H
bond
silanes,
C-O
ester,
silyl
ether
intermediates
by
is
crucial
achieving
exhaustive
reduction.
