A
three-component
reaction
of
trifluoromethyl
enones,
phosphine
oxides,
and
alcohols
in
water
solution
is
developed.
This
defluorinative
occurs
through
a
cascade
process
involving
defluorophosphorylation,
defluoroalkyloxylation,
defluoroheteroannulation,
enabling
the
modular
synthesis
furans
with
four
distinct
substituents:
C2-alkyloxy,
C3-trifluoromethyl,
C4-phosphoryl,
C5-(hetero)aryl
groups.
Moreover,
apart
from
alcohol
substrates,
scope
nucleophiles
could
be
further
extended
to
phenols,
azacycles,
or
sulfonamide.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(15), С. 2511 - 2515
Опубликована: Июль 4, 2023
Abstract
A
step‐economical
and
operationally
simple
nickel‐catalyzed
cross‐electrophile
coupling
of
aryl
phosphates
with
bromides
through
C−O
bond
cleavage,
which
precluded
the
employment
relatively
moisture‐labile
unreadily
available
organometallics,
was
developed.
The
reaction
proceeded
smoothly
in
presence
magnesium
turnings
lithium
chloride
THF
to
afford
corresponding
biaryls
moderate
good
yields
reasonable
functionality
tolerance.
ACS Catalysis,
Год журнала:
2023,
Номер
13(20), С. 13474 - 13483
Опубликована: Окт. 5, 2023
The
utilization
of
sulfinyl
sulfones
in
transition-metal-catalyzed
synthetic
chemistry
has
rarely
been
investigated.
Here
we
report
the
design
and
nickel-catalytic
conversion
situ-generated
redox-active
for
reductive
coupling
with
a
wide
variety
organic
halides
by
dual-role
nickel
catalyst
reductant
Zn.
Mechanistic
studies
disclose
that
key
such
reaction
is
employment
sulfones,
enabling
situ
generation
electrophilic
sulfur
reagents
through
zinc-induced
reduction
facilitated
catalyst.
This
strategy
demonstrates
good
tolerance
range
functional
groups.
Furthermore,
this
method
extends
to
meta-substituted
diaryl
sulfides,
modification
complex
bioactive
molecules
synthesis
thioether-containing
drugs.
Green Chemistry,
Год журнала:
2023,
Номер
25(5), С. 2000 - 2010
Опубликована: Янв. 1, 2023
A
highly
tunable
defluorophosphorylation
of
fluorinated
peroxides
for
the
preparation
C
3,4-diphosphoryl
furans
and
4-monophosphoryl
under
conditions
with
no
added
transition
metals
is
disclosed.
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.
A
three-component
reaction
of
trifluoromethyl
enones,
phosphine
oxides,
and
alcohols
in
water
solution
is
developed.
This
defluorinative
occurs
through
a
cascade
process
involving
defluorophosphorylation,
defluoroalkyloxylation,
defluoroheteroannulation,
enabling
the
modular
synthesis
furans
with
four
distinct
substituents:
C2-alkyloxy,
C3-trifluoromethyl,
C4-phosphoryl,
C5-(hetero)aryl
groups.
Moreover,
apart
from
alcohol
substrates,
scope
nucleophiles
could
be
further
extended
to
phenols,
azacycles,
or
sulfonamide.
