Abstract
Herein,
we
have
reported
a
sustainable
and
chemo‐selective
strategy
for
the
synthesis
of
functionalized
branched
alcohols.
A
commercially
available
catalytic
system
does
not
need
any
special
ligand
liberated
water
hydrogen
as
side
products.
series
alkyl
primary
alcohols
(C4–C10),
including
methanol,
were
tolerated
in
good
to
high
yield.
Sequential
transformations
substituted
pyrroles,
chromenes
donepezil
drug
obtained
(>57
entries).
Preliminary
mechanistic
investigations
performed
understand
pathways.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 23338 - 23347
Опубликована: Авг. 6, 2024
A
single-atom
iron
catalyst
was
found
to
exhibit
exceptional
reactivity
in
acceptorless
dehydrogenative
coupling
for
quinoline
synthesis,
outperforming
known
homogeneous
and
nanocatalyst
systems.
Detailed
characterizations,
including
aberration-corrected
HAADF-STEM,
XANES,
EXAFS,
jointly
confirmed
the
presence
of
atomically
dispersed
centers.
Various
functionalized
quinolines
were
efficiently
synthesized
from
different
amino
alcohols
a
range
ketones
or
alcohols.
The
achieved
turnover
number
(TON)
up
10
Dalton Transactions,
Год журнала:
2024,
Номер
53(7), С. 3236 - 3243
Опубликована: Янв. 1, 2024
A
quinoline-based
pincer
Mn
catalyst
for
α-alkylation
of
methyl
ketones
using
primary
alcohols
as
alkyl
surrogates
is
presented.
The
C–C
bond
formation
reaction
proceeds
via
a
hydrogen
auto-transfer
protocol,
generating
water
the
only
by-product.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5788 - 5793
Опубликована: Июнь 27, 2024
Stereocontrolled
oxa-Michael
additions
are
challenging,
given
the
high
reversibility
of
process,
which
ultimately
leads
to
racemization
newly
formed
stereocenters.
When
iron-catalyzed
borrowing
hydrogen
from
allylic
alcohols
was
combined
with
a
stereocontrolled
organocatalytic
addition,
wide
array
chiral
tetrahydropyrans
were
efficiently
prepared.
The
reaction
could
be
performed
in
diastereoselective
manner
pre-existing
stereocenters
or
enantioselectively
achiral
substrates.
key
success
reactivity
iron
complex,
selective
for
alcohol
dehydrogenation
and
irreversibly
led
final
product.
ACS Catalysis,
Год журнала:
2024,
Номер
14(10), С. 7795 - 7805
Опубликована: Май 6, 2024
Discovering
active,
cheap
iron
complexes
for
eco-compatible
borrowing
hydrogen
transformations
constitutes
a
real
challenge.
In
this
context,
we
developed
family
of
isonitrile-substituted
cyclopentadienone
complexes.
They
were
successfully
applied
in
traditional
amine
alkylation
with
alcohols
and,
notably,
the
development
photoactivated
multicatalytic
enantioselective
allylic
alcohol
functionalization.
Of
importance,
catalyst
showing
greater
activity
under
photoirradiation
differs
from
one
most
active
conventional
using
chemical
activation.
This
underscores
importance
incorporating
isonitrile
ligands
readily
customizable
manner,
resulting
catalysts
complementary
reactivities.
The
characterization
their
physical
properties
was
complemented
by
density
functional
theory
calculations
to
enhance
our
understanding
behavior.
Given
distinctive
disclosed
catalysts,
application
is
poised
pave
way
exploring
challenging
reactivities
related
catalytic
processes.
Organic Letters,
Год журнала:
2022,
Номер
24(44), С. 8180 - 8185
Опубликована: Окт. 28, 2022
Herein,
we
demonstrate
a
visible
light-induced
selenium
radical-mediated
domino
reaction
of
aryl
alkynoates,
for
the
synthesis
1,1-diselenide
alkene
derivatives
and
selenium-containing
α,β-unsaturated
carboxylic
acid.
The
process
is
mild,
metal
free,
easy
to
handle,
scalable.
decarboxylation
step
can
be
controlled
by
applying
catalytic
amount
Eosin
Y
dye
cesium
carbonate
as
base.
methodology
shows
good
functional
group
tolerance
provides
decent
yields
products.
In
addition,
synthetic
utility
this
protocol
was
expanded
further
preparing
allylic
alcohol,
ester,
vinylic
halides.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(4), С. 1386 - 1386
Опубликована: Янв. 1, 2023
In
recent
years,
the
development
and
application
of
transition
metal
ruthenium
or
iridium
complexes
based
photocatalysts
have
opened
up
a
new
research
field
for
organic
synthesis,
which
provides
mild
efficient
strategies
construction
chemical
bonds
transformations.In
order
to
enrich
types
photocatalysts,
broaden
scope
photocatalysis,
develop
green
sustainable
chemistry,
some
low-cost
easily
available
organometallic
with
copper
iron
were
applied
as
recently.Iron-complexes
feature
non-toxicity,
rich
variety,
unique
property
charge
transfer
from
ligands
metals,
enable
them
show
extraordinary
capability
in
photocatalytic
synthesis.According
different
reaction
types,
this
review
focuses
on
photoinduced
iron-catalysis
synthesis
including
C-H
bond
functionalization,
C-C
bifunctionalization
alkenes,
cross-coupling
reaction,
decarboxylative
selective
oxidation
reduction.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(11), С. 7498 - 7503
Опубликована: Май 23, 2023
We
report
a
class
of
quaternary
ammonium
Cinchona-functionalized
crown
ether-strapped
calix[4]arene
phase-transfer
catalysts
for
the
efficient
enantioselective
α-alkylation
glycine
imines.
The
catalyst
exhibits
excellent
catalytic
performance
at
0.1
mol
%
loading,
affording
desired
α-alkylated
glycinates
with
98%
yield
and
99.9%
ee.
could
be
recovered
recycled
up
to
30
test
cycles
without
significant
drop
in
activity.
Organometallics,
Год журнала:
2023,
Номер
42(14), С. 1784 - 1792
Опубликована: Июнь 1, 2023
The
reductive
amination
reaction
of
imines
catalyzed
by
Knölker-type
iron
complexes
under
hydrogen
at
high
pressure
is
very
interesting
in
synthetic
terms.
This
type
an
important
catalytic
challenge,
since
harsh
conditions
are
necessary
and
do
not
occur
easily.
In
a
previous
work
(
Organometallics
2022,
41,
1204−1215),
we
carried
out
computational
study
the
mechanism
showing
that
electron-withdrawing
groups
(EWGs)
attached
to
cyclopentadienone
favor
imines.
synthesis
with
cyclopentadienones
having
EWGs
straightforward,
direct
bonding
on
would
lead
but
undesired
dimerization.
A
possible
solution
consists
addition
phenyl
substituents
these
catalysts
then
introduction
rings.
We
have
performed
studies
using
density
functional
theory
(DFT)
for
analyze
efficiency
such
approach.
found
some
facilitate
result
has
been
later
confirmed
experimentally,
therefore,
computationally
designed
new
improve
performances
previously
known
complexes.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 15, 2024
Abstract
Hydrogen
borrowing
is
an
attractive
and
sustainable
strategy
for
carbon–carbon
bond
formation
that
enables
alcohols
to
be
used
as
alkylating
reagents
in
place
of
alkyl
halides.
However,
despite
intensive
efforts,
limited
functional
group
tolerance
observed
this
methodology,
which
we
hypothesize
due
the
high
temperatures
harsh
basic
conditions
often
employed.
Here
demonstrate
room
temperature
tolerant
hydrogen
can
achieved
with
a
simple
iridium
catalyst
presence
substoichiometric
base
without
excess
reagents.
Achieving
yields
necessitates
application
anaerobic
counteract
oxygen
sensitivity
catalytic
hydride
intermediate,
otherwise
leads
degradation.
Substrates
containing
heteroatoms
capable
complexing
exhibit
reactivity,
but
moderately
higher
extension
broad
range
medicinally
relevant
nitrogen
rich
heterocycles.
These
newly
developed
allow
possessing
groups
were
previously
incompatible
reactions
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 18032 - 18044
Опубликована: Ноя. 22, 2024
Selective
direct
alkylation
of
indenes
is
important
for
the
synthesis
and
decoration
indene
derivatives.
In
contrast
to
traditional
methods,
using
unactivated
alcohol
as
reagents
via
borrowing
hydrogen
or
autotransfer
highly
attractive.
However,
nature
high-lying
lowest
unoccupied
molecular
orbital
condensation
intermediate
raises
a
big
challenge
development
BH
system
alcohols.
Through
tuning
stability
reactivity
metal-hydride
species
by
theoretical
prediction,
herein,
we
succeeded
in
developing
non-noble
Mn-catalyzed
selective
monoalkylation
dialkylation
under
mild
conditions,
producing
corresponding
versatile
alkylated
satisfactory
yields.
A
broad
scope
substrates
including
primary
benzylic,
aliphatic,
amino,
hydroxyl,
second
alcohols
well
various
are
tolerated
system.
Additionally,
this
method
could
be
used
potential
precatalyst
complexes
bioactive
molecules.
Mechanistic
studies
control
experiments,
kinetic
investigations,
isotope
effect,
deuterium
labeling
density
functional
theory
calculations,
reveal
proper
successful
process.