Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 23, 2025
Alcohols
and
aryl
carboxylic
acids
are
among
the
most
commercially
abundant,
synthetically
versatile,
operationally
convenient
building
blocks
in
organic
chemistry.
Despite
their
widespread
availability,
direct
formation
of
C(sp3)-C(sp2)
bonds
from
these
functional
groups
remains
a
challenge.
Recently,
our
group
developed
robust
protocols
to
harness
alcohols
as
alkyl
radical
precursors,
but
activation
relatively
unexplored.
Herein,
we
describe
merger
N-heterocyclic
carbene
(NHC)-mediated
deoxygenation
nickel-mediated
decarbonylation
toward
bond
formation.
The
utility
this
method
is
demonstrated
through
synthesis
diverse
range
aryl-alkyl
cross-coupled
products
late-stage
functionalization
complex
molecules,
including
drugs,
natural
products,
biomolecules.
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15088 - 15093
Опубликована: Июль 3, 2023
The
first
practical,
fully
stereoselective
P(V)-radical
hydrophosphorylation
is
presented
herein
by
using
simple,
limonene-derived
reagent
systems.
A
set
of
reagents
have
been
developed
that
upon
radical
initiation
react
smoothly
with
olefins
and
other
acceptors
to
generate
P-chiral
products,
which
can
be
further
diversified
(with
conventional
2e–
chemistry)
a
range
underexplored
bioisosteric
building
blocks.
reactions
wide
scope
excellent
chemoselectivity,
the
unexpected
stereochemical
outcome
has
supported
computationally
experimentally.
Initial
ADME
studies
are
suggestive
promising
properties
this
rarely
explored
chemical
space.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 8, 2024
Abstract
Cross‐electrophile
coupling
(XEC)
between
aryl
halides
and
alkyl
is
a
streamlined
approach
for
C(sp
2
)−C(sp
3
)
bond
construction,
which
highly
valuable
in
medicinal
chemistry.
Based
on
key
Ni
II
amido
intermediate,
we
developed
selective
scalable
Ni‐catalyzed
electrochemical
XEC
reaction
(hetero)aryl
primary
secondary
halides.
Experimental
computational
mechanistic
studies
indicate
that
an
amine
ligand
slows
down
the
oxidative
addition
process
of
Ni‐polypyridine
catalyst
to
bromide
intermediate
formed
situ
during
process.
The
relatively
slow
beneficial
enhancing
selectivity
reaction.
stabilizes
–aryl
species
prevent
aryl–aryl
homo‐coupling
side
reactions
acts
as
activate
substrates.
This
electrosynthesis
system
provides
facile,
practical,
platform
formation
(hetero)aryl–alkyl
bonds
using
standard
catalysts
under
mild
conditions.
insights
from
this
work
could
serve
great
foundation
future
cross‐couplings.
Chemical Communications,
Год журнала:
2024,
Номер
60(17), С. 2405 - 2408
Опубликована: Янв. 1, 2024
Nickel-catalysed
chelation-assisted
reductive
cross-coupling
of
trifluoropropanamides/esters
with
disulfides
to
afford
thioacrylamides/esters
high
E
selectivity,
involving
triple
C–F
bond
cleavage.
Organic Letters,
Год журнала:
2024,
Номер
26(7), С. 1332 - 1337
Опубликована: Фев. 8, 2024
We
disclosed
a
Ni/CPA
cocatalyzed
protocol
to
access
diverse
C-acyl
glycosides
under
mild
conditions
with
broad
functional
group
compatibility
through
the
coupling
of
readily
available
glycosyl
bromides
and
carboxylic
esters.
The
potential
application
methodology
was
demonstrated
by
glycosylation
bioactive
molecules
transformation
products
variety
value-added
molecules.
Mechanistic
studies
revealed
that
CPA
might
serve
as
bifunctional
H-bond
catalyst
activate
esters
nickel
catalyst.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(23), С. 4233 - 4240
Опубликована: Окт. 27, 2023
Abstract
A
nickel‐catalyzed
reductive
cross
coupling
reaction
of
carboxylic
acids
with
disulfides
is
described.
The
readily
available
and
inexpensive
acid
activated
in
situ
by
the
formation
a
mixed
anhydride.
transformation
occurs
at
room
temperature
wide
functional
group
tolerance
to
efficiently
generate
structurally
diverse
thioesters.
Moreover,
tolerated
broad
substrate
scope,
including
sterically
hindered
disulfides.
Ultimately,
this
powerful
method
could
be
applied
late‐stage
functionalization
for
construction
thioesters,
affording
convenient
practical
tactic
construct
carbon‐sulfur
bonds.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3012 - 3018
Опубликована: Янв. 1, 2024
Herein,
we
report
a
decarbonylative
C(sp
2
)–C(sp
)
reductive
cross-coupling
of
aroyl
fluorides
with
aryl
bromides
by
palladium
and
cobalt
co-catalysis.
