Chemistry - An Asian Journal,
Год журнала:
2022,
Номер
17(23)
Опубликована: Сен. 26, 2022
Ru(II)-catalyzed
C-H
bond
activation
strategy
has
been
capitalized
through
a
(4+2)
annulative
difunctionalization
of
non-conjugated
alkenyl
amides.
Under
mild
conditions,
broad
range
(hetero)aromatic
amides
embedded
with
NH-OMe
unit
as
an
internal
oxidant
produced
high-value
dihydroisoquinolinone
scaffolds
in
good
to
excellent
yields.
This
heteroannulation
is
also
effective
acrylamides
dispense
dihydro-2-pyridones
and
accommodates
bioactive
such
tocopherol,
estrone,
amino
acids.
The
construction
of
C-S
bonds
has
garnered
significant
interest
due
to
the
ubiquitous
presence
organosulfur
compounds
in
natural
products
and
bioactive
molecules.
Herein,
we
report
a
one-pot,
stepwise
desulfuration
strategy
employing
trisulfides
as
precursors
for
synthesis
unsymmetrical
dialkylthioethers.
Our
study
demonstrates
that
copper
powder
facilitates
conversion
into
disulfides,
which
subsequently
undergo
nickel-catalyzed
reductive
coupling
afford
desired
products.
This
approach
provides
practical,
odorless,
broadly
applicable
method
ACS Catalysis,
Год журнала:
2022,
Номер
12(10), С. 6081 - 6091
Опубликована: Май 6, 2022
The
intramolecular
carbothiolation
of
unsaturated
hydrocarbons
using
a
palladium–NHC
catalyst
(NHC
=
N-heterocyclic
carbene)
is
described.
Herein,
single
system
enables
both
initial
activation
C(sp2)–S
bond
through
oxidative
addition
and
formation
C(sp3)–S
terminal
reductive
elimination,
unlocking
completely
atom-economical
transfer
across
alkenes.
reaction
tolerates
variety
different
functional
groups,
exhibits
excellent
chemoselectivity
in
the
presence
competing
thioether
moieties,
can
be
applied
to
various
alkenes
alkynes.
Furthermore,
product
derivatization
was
demonstrated
access
broad
sulfur-containing
compounds.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(2)
Опубликована: Ноя. 7, 2022
Shuttle
hetero-difunctionalization
reaction,
in
which
two
chemically
distinct
functional
groups
are
transferred
between
molecules,
has
long
been
an
unmet
goal
due
to
the
daunting
challenges
controlling
chemo-,
regio-,
and
stereoselectivity.
Herein,
we
disclose
electrochemistry
enabled
shuttle
reaction
(e-shuttle)
selectively
transfer
one
RS-
X-
group
β-halosulfides
unsaturated
hydrocarbons
via
a
consecutive
paired
electrolysis
mechanism.
The
preferential
anodic
oxidation
of
anion
over
other,
is
controlled
by
their
redox
potentials,
plays
pivotal
role
high
chemoselectivity
process.
This
easily
scalable
methodology
enables
construction
myriad
densely
functionalized
β-halo
alkenyl
sulfides
unprecedented
stereoselectivity
using
benign
surrogates,
e.g.,
2-bromoethyl
sulfide,
avoiding
handling
corrosive
oxidative
RS-Br
reagents.
In
broader
context,
these
results
open
up
new
strategies
for
selective
difunctionalization
reactions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Сен. 14, 2023
Geminal
cross
couplings
using
multiple
components
enable
the
formation
of
several
different
bonds
at
one
site
in
building
tertiary
and
quaternary
alkanes.
Nevertheless,
there
are
remaining
issues
concern-cleavage
two
geminal
control
selectivity
present
challenges.
We
report
here
three
by
reactions
dihaloalkanes
with
organomagnesium
chlorosilanes
or
alkyl
tosylates
Cr
catalysis,
affording
C-C/C-Si
C-C/C-C
creation
The
catalyzed
low-cost
CrCl2
,
enabling
sluggishness
competitive
Kumada-type
side
homocouplings
Grignard
reagents,
achieving
high
chemoselectivity.
Experimental
theoretical
studies
indicate
that
C-halide
continuously
cleaved
to
afford
a
metal
carbene
intermediate,
which
couples
reagent,
followed
silylation,
C-C
C-Si
via
novel
inner-sphere
radical
coupling
mechanism.
These
three-component
value-addition
synthesis
commercial
drugs
bioactive
molecules
medicinal
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(33)
Опубликована: Июнь 17, 2023
Transition
metal-catalyzed
C-S
cross-coupling
has
emerged
as
an
important
strategy
to
furnish
thioethers;
however,
the
dominant
utilization
of
noble
metal
catalysts
well
construction
challenging
C(sp3
)-S
bonds
by
transition
metal-catalysis
remain
highly
problematic.
Earth-abundant
manganese
gathered
increasing
interest
attractive
catalyst
for
new
reaction
development;
nevertheless,
catalysis
not
been
reported.
Herein,
we
disclose
a
efficient
manganese-catalyzed
redox-neutral
thiolation
broad
range
alkyl
halides
with
thioformates
practical
sulfuration
agents.
Strategically,
employing
easily
synthesized
thiyl
radical
precursors
allows
access
various
aryl
and
thioethers
in
good
excellent
yields.
Notably,
this
method
avoids
strong
bases,
external
ligands,
forcing
conditions,
stoichiometric
manganese,
thus
presenting
apparent
advantages,
such
substrate
scope,
functional
group
compatibility,
mild
conditions.
Finally,
utilities
are
also
illustrated
downstream
transformations
late-stage
structurally
complex
natural
products
pharmaceuticals.
Organic Letters,
Год журнала:
2022,
Номер
24(36), С. 6642 - 6646
Опубликована: Сен. 6, 2022
We
report
a
C–N
cross-coupling
reaction
of
weakly
nucleophilic
N-arylsulfonamides
and
aryl
bromides
to
access
N,N-diarylsulfonamides
using
Ni(cod)(DQ)
as
catalyst
without
additional
ligands.
The
process
is
compatible
with
electron-deficient
electron-rich
heteroaryl
(34
examples,
21–98%)
can
be
applied
the
derivatization
an
N-arylsulfonamide
pharmaceutical
compound.
Chemical Science,
Год журнала:
2022,
Номер
13(22), С. 6567 - 6572
Опубликована: Янв. 1, 2022
We
report
a
regioselective,
nickel-catalyzed
syn-1,2-carbosulfenylation
of
non-conjugated
alkenyl
carbonyl
compounds
with
alkyl/arylzinc
nucleophiles
and
tailored
N-S
electrophiles.
This
method
allows
the
simultaneous
installation
variety
C(sp3)
S(Ar)
(or
Se(Ar))
groups
onto
unactivated
alkenes,
which
complements
previously
developed
1,2-carbosulfenylation
methodology
in
only
C(sp2)
are
compatible.
A
bidentate
directing
auxiliary
controls
regioselectivity,
promotes
high
syn-stereoselectivity
E-
Z-internal
enables
use
an
array
electrophilic
sulfenyl
(and
seleno)
Among
compatible
electrophiles,
those
N-alkyl-benzamide
leaving
were
found
to
be
especially
effective,
as
determined
through
comprehensive
structure-reactivity
mapping.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(6)
Опубликована: Янв. 3, 2023
Abstract
Herein,
we
report
a
palladium/norbornene/copper
co‐catalyzed
single‐step
approach
that
merges
selective
ortho
C−H
bond
esterification
with
ipso
thiolation
for
construction
of
synthetically
versatile
2‐arylthio
aryl
esters
under
exceptionally
mild
conditions.
Importantly,
this
process
proceeded
in
highly
efficient
manner,
allowing
alkoxycarbonyl
and
thio
groups
to
be
installed
into
one
iodides
simultaneously
by
harnessing
thiocarbonate
as
bifunctional
reagent.
The
method
has
been
demonstrated
accommodate
good
functionalities
features
broad
substrate
scope.
