Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Comprehensive
Summary
The
transition
metal‐catalyzed
acceptorless
dehydrogenative
coupling
of
alcohols
and
amines
is
one
the
attractive
important
strategies
for
construction
C=N
bonds
from
perspective
environmental
friendliness
economy.
Herein,
we
report
synthesis
four
novel
phosphine‐free
cobalt(II)
complexes
(
Co‐1
—
Co‐4
)
with
N,O‐bidentate
ligands
incorporating
N‐oxide
units
their
catalytic
activity
in
benzylic
aryl
amines.
X‐ray
diffraction
analyses
revealed
that
central
cobalt
atoms
three
,
Co‐2
were
six‐coordinated
adopted
an
octahedral
geometry
configuration.
Catalytic
evaluation
demonstrated
exhibited
higher
than
other
complexes.
This
system
could
provide
a
series
corresponding
imine
products
good
functional
groups
compatibility
high
yields.
Especially,
use
inexpensive
complexes,
along
readily
accessible
featuring
moieties,
offers
significant
advantages
this
reaction.
Chemical Reviews,
Год журнала:
2024,
Номер
124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 22, 2024
Abstract
N-Glycosylated
heterocycles
play
important
roles
in
biological
systems
and
drug
development.
The
synthesis
of
these
compounds
heavily
relies
on
ionic
N-glycosylation,
which
is
usually
constrained
by
factors
such
as
labile
glycosyl
donors,
precious
metal
catalysts,
stringent
conditions.
Herein,
we
report
a
dehydroxylative
radical
method
for
synthesizing
N
-glycosides
leveraging
copper
metallaphotoredox
catalysis,
stable
readily
available
1-hydroxy
carbohydrates
are
activated
direct
N-glycosylation.
Our
employs
inexpensive
photo-
copper-
catalysts
can
tolerate
some
extent
water.
reaction
exhibits
broad
substrate
scope,
encompassing
76
examples,
demonstrates
high
stereoselectivity,
favoring
1,2-
trans
selectivity
furanoses
α-selectivity
pyranoses.
It
also
site-selectivity
substrates
containing
multiple
N-atoms.
synthetic
utility
showcased
through
the
late-stage
functionalization
bioactive
pharmaceuticals
like
Olaparib,
Axitinib,
Metaxalone.
Mechanistic
studies
prove
presence
radicals
importance
catalysis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13451 - 13496
Опубликована: Авг. 26, 2024
Alcohols
are
abundant
with
versatile
structural
variety
and
have
ample
use
as
pivotal
functional
groups
in
numerous
organic
processes.
Because
of
their
frequent
occurrence
enumerable
natural
products,
bioactive
molecules,
medicinal
components,
alcohol
functionalities
provide
a
promising
scope
research
to
advance
the
operational
diversity
for
improving
clinical
success.
Recent
years
witnessed
design
modern
C–C
C–heteroatom
bond-forming
approaches
easily
accessible
commercially
available
unactivated
aliphatic
alcohols
native
adaptive
sp3
handles,
hence
offering
groundbreaking
transformative
pathways
functionalization
complex
molecular
architectures.
The
judicial
application
appropriate
activating
generate
alkyl
radical
from
through
C–O
bond
fragmentation
employ
it
potential
alkylating
agent
unfolds
unique
synthetic
strategies,
thereby
replacing
obvious
requirement
halides.
This
review
elaborately
discusses
recent
trends
regarding
using
C(sp3)-centered
various
chemical
transformations
by
exploiting
different
activation
modes
disrupter
under
photoredox
catalysis.
presentation
is
organized
nature
scaffolds,
kind
formation,
progress
achieved
this
domain
since
original
discovery
providing
illustrative
examples
mechanistic
details,
focus
on
difficulties
future
prospects.
Although
alkyl
alcohols
and
aryl
chlorides
are
the
two
most
abundant
substrate
pools
for
cross-electrophile
coupling,
methods
to
couple
them
remain
limited.
Herein
we
demonstrate
a
simple
procedure
in
situ
deoxychlorination
of
followed
by
XEC
with
chlorides.
A
broad
scope
can
be
achieved
tuning
rate
reaction
via
halide
exchange.
Key
success
is
identification
1-chloro-N,N,2-trimethyl-1-propenylamine
as
mild,
noninterfering
halogenation
reagent.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 30, 2025
The
direct
cross-couplings
of
aryl
nonaflates
with
bromides
could
be
successfully
accomplished
by
utilizing
nickel
as
the
catalyst,
magnesium
metal
mediator,
and
lithium
chloride
additive.
reactions
proceeded
efficiently
in
THF
at
room
temperature
to
produce
desired
biaryls
moderate
good
yields,
showing
both
a
reasonable
substrate
scope
functional
group
tolerance.
Additionally,
an
equally
performance
realized
when
reaction
was
subjected
scale-up
synthesis.
Preliminary
study
suggested
that
presumably
proceeds
through
situ
formation
arylmagnesium
reagent
key
intermediate.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(24), С. 3539 - 3546
Опубликована: Авг. 19, 2023
Comprehensive
Summary
Cross‐electrophile
coupling
of
triazine
esters
with
aryl
bromides
could
be
facilely
accomplished
by
employing
nickel
as
catalyst,
magnesium
metal
mediator,
and
lithium
chloride
additive.
The
reactions
proceeded
efficiently
in
THF
at
room
temperature
through
C—O
bond
activation
to
afford
an
array
structurally
different
diaryl
ketones
moderate
good
yields
wide
functional
group
tolerance.
Control
experiments
showed
that
nickel,
magnesium,
chloride,
are
all
indispensable
for
the
performance
reaction.
Preliminary
mechanistic
exploration
indicated
situ
formed
arylmagnesium
reagent
insertion
into
bromide
might
serve
key
intermediate
cross‐coupling.
method
which
avoids
utilization
moisture‐labile
relatively
difficult‐to‐obtain
organometallics
is
step‐economical,
cost‐efficient,
operationally
simple,
potentially
serving
attractive
alternative
documented
methods.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 28, 2024
Abstract
Transition
metal-catalyzed
enantioconvergent
cross-coupling
of
an
alkyl
precursor
presents
a
promising
method
for
producing
enantioenriched
C(sp
3
)
molecules.
Because
alcohol
is
ubiquitous
and
abundant
family
feedstock
in
nature,
the
direct
reductive
coupling
aryl
halide
enables
efficient
access
to
valuable
compounds.
Although
several
strategies
have
been
developed
overcome
high
bond
dissociation
energy
C
−
O
bond,
asymmetric
pattern
remains
unknown.
In
this
report,
we
describe
realization
deoxygenative
unactivated
(β-hydroxy
ketone)
bromide
presence
NHC
activating
agent.
The
approach
can
accommodate
substituents
various
sizes
functional
groups,
its
synthetic
potency
demonstrated
through
gram
scale
reaction
derivatizations
into
other
compound
families.
Finally,
apply
our
convergent
synthesis
four
β-aryl
ketones
that
are
natural
products
or
bioactive
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(18), С. 13601 - 13607
Опубликована: Сен. 4, 2024
A
zinc-mediated
cross-electrophile
coupling
of
benzyl
sulfonium
salts
with
thiosulfonates
via
C-S
bond
cleavage
was
achieved.
The
reductive
thiolation
proceeded
well
under
transition
metal-free
conditions
to
afford
the
desired
sulfides
in
good
yields,
exhibiting
both
broad
substrate
scope
and
functionality
tolerance.
In
addition,
reaction
could
be
applied
use
selenosulfonate
as
an
effective
selenylation
agent
subjected
scale-up
synthesis.
