Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(3), С. 518 - 525
Опубликована: Дек. 29, 2023
Abstract
A
ruthenium‐catalyzed
C(
sp
2
)−H
acyloxylation
of
2‐aroyl
pyridine
derivatives
with
simple
sodium
carboxylate
utilizing
transformable
directing
groups
is
described.
This
protocol
features
broad
functional
group
tolerance
and
chemo‐
regio‐selectivity,
providing
the
products
in
45%‐84%yield.
Furthermore,
synthetic
utility
this
was
demonstrated
by
late‐stage
functionalization
pharmaceutical
compounds.
Notably,
could
be
further
transformed
into
a
variety
useful
heterocycles
under
mild
conditions.
Reductive
functionalization
of
aldehydes
and
ketones
is
one
the
most
challenging
but
ultimately
rewarding
areas
in
synthetic
chemistry
related
sciences.
We
report
a
simple
extremely
versatile
carbonyl
reductive
strategy
achieving
direct,
highly
selective,
efficient
amination,
etherification,
esterification,
phosphinylation
reactions
(hetero)aryl
ketones,
which
are
or
unattainable
to
achieve
by
traditional
strategies,
using
only
diphenylphosphine
oxide
an
inorganic
base.
It
enables
modular
synthesis
functionally
structurally
diverse
tertiary
amines,
ethers,
esters,
phosphine
oxides,
etc.,
as
well
pesticides,
drug
intermediates,
pharmaceuticals.
Compared
phosphorus-mediated
name
reactions,
this
firstly
transformed
C═O
bonds
into
C-element
single
bonds.
Mechanistically,
phosphinates
formed
undergo
unconventional
nucleophilic
substitution
at
C
atom
within
their
C─O─P
unit.
Thus,
work
provides
important
strides
field
aldehydes/ketones,
transformation,
various
fundamental
reactions.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(3)
Опубликована: Янв. 30, 2023
Abstract
The
[1,2]‐phospha‐Brook
rearrangement
involves
the
migration
of
dialkoxyphosphoryl
moiety
alkoxide
an
α‐hydroxyphosphonate
from
carbon
to
oxygen
generate
α‐oxygenated
carbanion.
that
is
precursor
for
easily
accessible
by
deprotonation
α‐hydroxyphosphonates
or
addition
anion
secondary
phosphites
carbonyl
compounds
under
influence
a
Brønsted
base.
This
review
article
summarized
recent
development
base‐catalyzed
reactions
in
which
utilized
generation
carbon‐based
anionic
nucleophiles.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(12), С. 1747 - 1760
Опубликована: Май 31, 2024
ConspectusAromatic
esters
are
cost-effective,
versatile,
and
commonly
used
scaffolds
that
readily
synthesized
or
encountered
as
synthetic
intermediates.
While
most
conventional
reactions
involving
these
nucleophilic
acyl
substitutions
1,2-nucleophilic
additions─where
a
nucleophile
attacks
the
carbonyl
group,
decarbonylative
transformations
offer
an
alternative
pathway
by
using
group
leaving
group.
This
transition-metal-catalyzed
process
typically
begins
with
oxidative
addition
of
C(acyl)–O
bond
to
metal.
Subsequently,
reaction
involves
migration
CO
metal
center,
nucleophile,
reductive
elimination
yield
final
product.
Pioneering
work
Yamamoto
on
nickel
complexes
development
(such
Mizoroki–Heck-type
olefination)
aromatic
carboxylic
anhydrides
catalyzed
palladium
were
conducted
de
Vries
Stephan.
Furthermore,
reports
have
surfaced
hydrogenation
pyridyl
methyl
Murai
ruthenium
catalysts
well
nitro
phenyl
Gooßen
under
catalysis.
Our
has
been
at
forefront
developing
C–H
arylations
1,3-azoles
aryl
boronic
acids
catalysts.
The
key
this
is
use
esters,
which
easy
synthesize,
stabilize,
handle,
allowing
bond;
nickel,
facilitates
suitable
bidentate
phosphine
ligands
can
stabilize
intermediate.
By
modification
nucleophiles,
effectively
utilized
electrophiles
in
cross-coupling
reactions,
encouraging
nucleophiles
among
researchers.
Account
summarizes
our
advancements
for
coupling
particularly
highlighting
utilization
diverse
such
alkenylation,
intramolecular
etherification,
α-arylation
ketones,
arylation,
methylation,
arylation
dibenzofuran
synthesis,
along
cyanation
coupling.
We
also
delve
into
types
distinct
from
typical
including
ester
dance
ring
exchanges,
deoxygenative
transformations,
focusing
complex.
For
example,
hypothesized
undergo
1,2-translocation
starting
complex,
leading
sequence
ortho-deprotonation/decarbonylation,
followed
protonation,
carbonylation,
elimination.
exchange
likely
different
In
coupling,
complex
engages
forming
intermediate
undergoes
presence
appropriate
reducing
agent.
These
methodologies
poised
captivate
interest
chemists
offering
unconventional
emerging
approaches
transforming
esters.
Moreover,
we
demonstrated
potential
transform
available
basic
chemicals
new
compounds
through
organic
synthesis.
Green Chemistry,
Год журнала:
2024,
Номер
26(3), С. 1375 - 1380
Опубликована: Янв. 1, 2024
A
visible-light-mediated
tandem
ring
opening/1,6-conjugate
addition
of
cyclobutanols
with
p
-quinone
methides
was
developed.
This
protocol
allowed
the
formation
δ,δ-diaryl
ketones
in
presence
a
readily
available
organic
photocatalyst.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(5), С. 932 - 939
Опубликована: Янв. 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.
Abstract
3‐Methylene‐substituted
oxindoles
play
crucial
roles
as
pharmaceutically
important
reagents
well
valuable
synthons
in
medicinal
and
organic
synthesis.
In
this
study,
a
uniform
nucleophilic
vinylic
substitution
(S
N
V)
reaction
for
the
construction
of
phosphonyl
sulfonyl
substituted
3‐methylene‐oxindole
was
developed
with
application
(
E
)‐3‐(nitromethylene)
oxindole
powerful
precursor.
addition,
preliminary
study
revealed
that
these
have
potential
applications
both
constructing
intriguing
molecules
serving
antibacterial
agents.
Tf2NH-mediated
regio-
and
diastereoselective
skeletal
metamorphosis
of
1-alkynyl-2,3-diaryl-2-methoxycarbonylcyclopropyl
ketones
readily
gave
2,3,4,5-tetraaryl-2,3-dihydrofurans.
Controllable
reduction
removal
the
ester
group
then
precisely
afforded
four
types
eight
possible
tetrahydrofuran
(THF)
diastereomers
with
different
(hetero)aryl
substituents.
Further,
deuterium-labeling
results
revealed
an
unprecedented
hydrogen
transfer
from
formyl
C-H
bond
in
tBuOK-promoted
decarbonylation
under
tBuOH-free
conditions.
Herein,
we
present
a
versatile
method
for
synthesizing
unsymmetrical
diarylmethanes
and
diarylketones
from
aldehydes
arenes.
This
involves:
(1)
regioselective
Ar-H
alkylation
to
form
benzhydrylphosphonium
salts
via
one-pot,
four-component
reaction
with
simple
reagents
(2)
chemoselective
reductions
or
oxidations
of
the
benzylic
C-P
bond.
Notably,
D2O
yield
fully
deuterated
diarylmethanes.
high-yielding,
straightforward
approach
offers
valuable
building
blocks
enables
novel
transformations
academic
pharmaceutical
research.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 8157 - 8167
Опубликована: Май 10, 2024
Direct
transformations
of
diarylketones
to
hetero-
and
carbofunctionalized
diarylmethanes
have
been
developed.
The
reactions
involve
a
phospha-Brook
rearrangement
diphenylphosphine
oxide
with
diarylketones,
followed
by
substitutions
various
nucleophiles
such
as
amides,
amines,
phenols,
thiols,
diborylmethane
under
palladium
catalysis
afford
the
corresponding
functionalized
in
reductive
manner.
Molecules,
Год журнала:
2025,
Номер
30(6), С. 1367 - 1367
Опубликована: Март 18, 2025
It
was
shown
for
the
first
time
that
diaryl(hetaryl)ketones
are
capable
of
directly
phosphorylating
with
red
phosphorus
in
superbase
suspension
KOH/DMSO(H2O)
at
85
°C
1.5
h
to
afford
potassium
bis(diaryl(hetaryl)methyl)phosphates
were
earlier
inaccessible
a
yield
up
45%.
The
ESR
data
demonstrate
unlike
previously
published
phosphorylation
elemental
phosphorus,
this
new
reaction
proceeds
via
single
electron
transfer
from
polyphospide
anions
diaryl(hetaryl)ketones.
This
is
example
C-O-P
bond
generation
during
strongly
basic
media,
which
usually
provides
C-P
formation.
