Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(42), P. 7689 - 7693
Published: Oct. 18, 2023
A
cross-electrophilic
coupling
of
benzyl
sulfonium
salts
with
alkyl
halides
forming
Csp3–Csp3
bonds
is
described
by
using
a
Co-based
catalytic
system.
The
activation
the
stable
Csp3–S
bond
under
mild
reaction
conditions
leads
to
various
functionalized
derivatives.
Preliminary
mechanistic
studies
suggest
involvement
radicals
formed
from
both
and
sulfoniums
through
single
electron
transfer.
European Journal of Inorganic Chemistry,
Journal Year:
2020,
Volume and Issue:
2020(26), P. 2486 - 2500
Published: April 30, 2020
This
minireview
aims
to
cover
the
developments
over
past
two
decades
in
chemistry
of
sulfonium
salts.
Specifically,
insight
is
provided
into
synthetic
strategies
available
for
preparation
these
compounds,
different
reactivity
patterns
that
are
expected
depending
on
their
structural
features
or
reaction
conditions
applied,
and
diversity
organic
scaffolds
can
thereby
be
synthesized.
Additionally,
pros
cons
derived
from
use
salts
presented
critically
compared,
when
possible,
relation
reagents
not
based
sulfur
but
depicting
similar
reactivity.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(19), P. 8351 - 8377
Published: Jan. 1, 2022
This
review
focuses
on
nickel-catalyzed
construction
and
transformation
of
various
sulfide-containing
compounds,
such
as
sulfides,
disulfides,
hypervalent
sulfur-containing
compounds.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(22), P. 9371 - 9423
Published: Jan. 1, 2022
The
transformation
of
carbon
dioxide
(CO2)
into
useful
chemicals,
advanced
materials,
and
energy
is
a
long-standing
challenge
in
both
fundamental
science
industry.
In
recent
years,
utilization
CO2
the
presence
inexpensive
non-negligible
environmentally
friendly
3d
metal-based
catalysts
(Fe,
Mn,
Co,
Ni,
Cu
Ti)
has
become
one
most
attractive
topics.
Particular
attention
been
given
to
synthesis
carboxylic
acids
their
derivatives
since
these
molecules
serve
as
key
intermediates
chemical,
fertilizer,
pharmaceutical
sectors.
Considering
numerous
challenges
linked
with
reactivity,
number
research
groups
have
recently
focused
on
by
following
thermo-,
photo-,
electrochemical
strategies.
However,
facile
access
such
remains
vital
catalysis
organic
owing
high
stability
molecule
which
atom
highest
oxidation
state.
Another
hurdle
solve
selectivity
issue
caused
reaction
different
catalytic
systems
reactive
functional
group-containing
molecules.
Despite
all
issues,
wide
range
transition
applied
this
direction,
but
cheaper
price
inherent
metals
are
at
forefront
domain.
these,
we
aim
summarise
advances
(over
past
five
years)
3d-metal
complexes
reactivity
towards
activation
for
acids.
Furthermore,
discuss
current
trends,
knowledge
gaps,
invigorating
perspectives
future
advances.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 9988 - 9993
Published: May 1, 2023
Herein,
a
regioselective,
late-stage
two-step
arene
halogenation
method
is
reported.
We
propose
how
unusual
Ni(I)/(III)
catalysis
enabled
by
combination
of
aryl
thianthrenium
and
Ni
redox
properties
that
hitherto
unachieved
with
other
(pseudo)halides.
The
catalyst
accessed
in
situ
from
inexpensive
NiCl2·6(H2O)
zinc
without
the
need
supporting
ligands.
Accounts of Chemical Research,
Journal Year:
2021,
Volume and Issue:
54(20), P. 3941 - 3952
Published: Sept. 29, 2021
ConspectusThe
ubiquity
and
importance
of
carboxylic
acids
amides
in
peptides,
pharmaceuticals,
agrochemicals,
synthetic
materials
has
challenged
chemists
to
design
de
novo
catalytic
carboxylation
amidation
protocols.
They
represent
a
powerful
alternative
canonical
oxidation
alcohols
aldehydes,
hydrolysis
nitriles,
transamidation
reactions,
or
condensation
techniques
for
the
synthesis
these
functional
groups.
Among
various
scenarios,
recent
years
have
witnessed
considerable
advances
Ni-catalyzed
reductive
reactions
utilizing
carbon
dioxide
isocyanate
counterparts.
This
Account
aims
highlight
progress
made
this
arena
with
historical
perspective,
particular
emphasis
on
methodologies
that
emanated
from
our
laboratories
without
losing
sight
underlying
principles
by
which
operate,
ultimate
goal
allowing
transition
comprehension
prediction
exciting
field.Unlike
utilization
conventional
polar
yet
highly
reactive
organometallic
reagents
nickel
catalysts
allowed
use
isocyanates
less
less-polarized
counterparts
formations
amides.
These
groups
include
organic
halides
pseudohalides
(i.e.,
alkyl
bromides
chlorides,
esters,
alcohols,
ammonium
salts),
unsaturated
hydrocarbons
alkynes,
styrenes,
unactivated
alkenes,
dienes)
even
C–H
bonds,
where
forging
targeted
C–C
bond
at
previously
unfunctionalized
linkages
was
possible,
thus
giving
access
densely
functionalized
compounds
would
be
difficult
otherwise.
The
functionalization
includes
chain-walking
subtle
changes
ligand
reaction
conditions
marked
selectivity
transformations,
via
[1,4]-Ni
shift,
selective
aromatic
rings
could
achieved.
Conceptuality
practicality
aside,
transformations
offered
possibility
modulating
dictating
site-selectivity
pattern,
providing
not
only
new
vistas
when
controlling
bond-forming
specific
sites
within
side
chain
but
also
knowledge
retrosynthetic
analysis
accessing
amide
backbones.
Importantly,
shown
particularly
suited
preparation
isotopically
labeled
molecules
using
13CO2
14CO2,
becoming
useful
endeavor
drug
discovery
pipeline.
Although
mechanistic
understanding
molecular
level
still
constitutes
"Achilles
heel"
empirical
discoveries
rapid
adoption
protocols
community
augurs
well
widespread
both
academic
industrial
laboratories.
The Chemical Record,
Journal Year:
2021,
Volume and Issue:
21(12), P. 3356 - 3369
Published: Jan. 7, 2021
Abstract
After
the
20‐year
dormant
period
since
Liebeskind's
seminal
report,
triorganosulfonium
salts
have
now
proved
to
be
reliably
useful
surrogates
of
or
complement
organic
halides
in
a
variety
transition‐metal‐catalyzed
transformations.
By
necessity,
my
group
developed
Suzuki‐Miyaura
ring‐opening
arylation
sulfonium
dibenzothiophenes
with
tetraarylborates
and
Pd‐catalyzed
intramolecular
C−H/C−S
coupling.
Following
this
starting
point
experiencing
decent
reactivity
salts,
order
maximize
synthetic
utility
organosulfur
compounds,
we
successfully
applied
readily
available
Ni‐catalyzed
coupling
arylzinc
reagents,
Pd‐
photoredox‐catalyzed
Mizoroki‐Heck
reaction,
alkoxycarbonylation,
Miyaura
borylation,
reductive
carboxylation,
zincation.
I
sincerely
hope
Personal
Account
will
facilitate
further
development
reactions
which
are
difficult
achieve
using
conventional
(pseudo)halides.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(11), P. 4400 - 4405
Published: May 19, 2021
A
highly
efficient
method
for
the
selective
formal
C-H/C-H
cross-coupling
of
azoles
and
(hetero)arenes
was
established
through
arylsulfonium
intermediates
under
transition-metal
catalysis,
which
produced
a
variety
2-(hetero)aryl
in
good
to
excellent
yields.
Advantages
reaction
included
mildness,
functional
group
tolerance,
wide
range
substrates,
high
regio-
chemoselectivity,
one-pot
procedures,
late-stage
functionalization
complex
molecules
without
use
oxidants,
offering
promising
strategy
transition-metal-catalyzed
C-H
arylation
azoles.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Oct. 5, 2022
Carboxyl
group
is
one
of
the
most
widely
used
groups
in
organic
synthesis.
Herein,
an
efficient
copper-catalyzed
carboxylation
aryl
thianthrenium
salts
with
carbon
dioxide
(CO2
)
at
room
temperature
has
been
developed.
The
reaction
employs
low
loading
cuprous
chloride
catalyst
under
1
atm
CO2
and
exhibits
good
functional
tolerance.
In
combination
C-H
thianthrenation
aromatic
hydrocarbons,
this
work
provides
method
for
site-selective
hydrocarbons.
It
may
serve
as
a
significant
late-stage
tool
modification
drug
molecules
future.
