Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(37)
Опубликована: Апрель 19, 2023
M-HAT
isomerization
is
a
highly
reliable
method
to
access
thermodynamically
stable
alkenes
with
high
functional
group
tolerance.
However,
synthesis
of
heteroatom-substituted
by
reaction
still
underdeveloped.
Herein,
we
report
an
enamide
using
via
combination
cobalt
and
photoredox
catalysis.
This
tolerates
variety
groups
including
haloarenes,
heteroarenes,
free
hydroxy
groups,
non-protected
indoles,
drug
derivatives.
Furthermore,
this
can
isomerize
styrene
derivatives
in
good
yield
E/Z
selectivity.
Science,
Год журнала:
2022,
Номер
376(6592), С. 527 - 532
Опубликована: Апрель 28, 2022
Discovery
chemists
routinely
identify
purpose-tailored
molecules
through
an
iterative
structural
optimization
approach,
but
the
preparation
of
each
successive
candidate
in
a
compound
series
can
rarely
be
conducted
manner
matching
their
thought
process.
This
is
because
many
necessary
chemical
transformations
required
to
modify
cores
straightforward
fashion
are
not
applicable
complex
contexts.
We
report
method
that
addresses
one
facet
this
problem
by
allowing
hop
directly
between
chemically
distinct
heteroaromatic
scaffolds.
Specifically,
we
show
selective
photolysis
quinoline
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15360 - 15369
Опубликована: Июль 10, 2023
Azetidines
are
prominent
structural
scaffolds
in
bioactive
molecules,
medicinal
chemistry,
and
ligand
design
for
transition
metals.
However,
state-of-the-art
methods
cannot
be
applied
to
intramolecular
hydroamination
of
allylic
amine
derivatives
despite
their
underlying
potential
as
one
the
most
prevalent
synthetic
precursors
azetidines.
Herein,
we
report
an
electrocatalytic
method
sulfonamides
access
azetidines
first
time.
The
merger
cobalt
catalysis
electricity
enables
regioselective
generation
key
carbocationic
intermediates,
which
could
directly
undergo
C-N
bond
formation.
mechanistic
investigations
including
electrochemical
kinetic
analysis
suggest
that
either
catalyst
regeneration
by
nucleophilic
cyclization
or
second
oxidation
intermediate
is
involved
rate-determining
step
(RDS)
our
protocol
highlight
ability
electrochemistry
providing
ideal
means
mediate
oxidation.
ACS Catalysis,
Год журнала:
2022,
Номер
12(24), С. 14806 - 14811
Опубликована: Ноя. 22, 2022
We
report
a
conceptually
distinct
strategy
for
the
synthesis
of
1,1-diarylalkanes
and
triarylalkanes.
Key
to
this
approach
is
use
light
simultaneously
trigger
(i)
formation
CoIII–H
species
which
undergoes
H
atom
transfer
(MHAT)
styrenes,
giving
carbon-centered
radical,
(ii)
generation
persistent
(hetero)arene
radical.
Selective
coupling
these
two
yields
Markovnikov
hydroarylation
products
under
mild
conditions
without
precious
metals.
In
contrast
many
previous
approaches,
electron-deficient
partners
are
favored
it
possible
construct
highly
congested
quaternary
centers,
including
those
with
three
different
aryl
groups.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(29), С. 15714 - 15720
Опубликована: Июль 12, 2023
Metal-hydride
hydrogen
atom
transfer
(MHAT)
has
emerged
as
a
useful
tool
to
form
quaternary
carbons
from
alkenes
via
hydrofunctionalization.
Methods
date
that
cross-couple
with
sp3
partners
rely
on
heterobimetallic
catalysis
merge
the
two
cycles.
Here,
we
report
an
iron-only
cross-coupling
putative
MHAT/SH2
steps
solves
key
stereochemical
problem
in
synthesis
of
meroterpenoid
eugenial
C
and
obviates
need
for
nickel.
The
concise
benefits
conformationally
locked
o,o′-disubstituted
benzyl
bromide
locally
sourced
chiral
pool
terpene
coupling
partner.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 4158 - 4165
Опубликована: Фев. 8, 2023
Metal–organic
layers
(MOLs),
a
monolayered
version
of
metal–organic
frameworks
(MOFs),
have
recently
emerged
as
novel
two-dimensional
molecular
material
platform
to
design
multifunctional
catalysts.
MOLs
inherit
the
intrinsic
tunability
MOFs
and
yet
more
accessible
modifiable
building
blocks.
Here
we
report
engineering
six
via
modulated
solvothermal
synthesis
between
HfCl4
three
photosensitizing
ligands
followed
by
postsynthetic
modification
with
two
carboxylate-containing
cobaloximes
for
tandem
synergistic
photocatalysis.
Morphological
structural
characterization
transmission
electron
microscopy
atomic
force
compositional
analysis
inductively
coupled
plasma-mass
spectrometry
nuclear
magnetic
resonance
spectroscopy
establish
flat
nanoplates
periodic
lattice
structure
hexagonal
symmetry.
The
efficiently
catalyze
dehydrogenative
coupling
reactions
Heck-type
reactions.
most
active
MOL
catalyst
was
used
gram-scale
vesnarinone,
cardiotonic
agent,
in
80%
yield
turnover
number
400
eight
consecutive
reaction
cycles
without
significant
loss
activities.
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 851 - 857
Опубликована: Янв. 21, 2025
The
prevalence
of
saturated
azacycles
within
pharmaceuticals,
natural
products,
and
agrochemicals
has
prompted
the
development
many
methods
that
modify
their
periphery.
In
contrast,
technologies
interconvert
distinct
azacyclic
frameworks,
which
would
uniquely
facilitate
access
to
underexplored
chemical
space,
are
highly
limited.
Existing
approaches
for
modifying
core
usually
require
either
installation
reactive
functionality,
must
later
be
removed
in
subsequent
steps,
or
use
tailored
substrates,
limiting
applicability
drug
discovery.
Herein,
we
report
a
borane-catalyzed
contraction
N-hydroxy
azacycles.
This
transformation
is
enabling,
allowing
reorganization
connectivity
substrate
without
altering
molecular
formula
generating
products
vestigial
functionality
derived
from
auxiliary
groups.
outcome
reductive
Stieglitz-type
can
attributed
key
stereoelectronic
interaction
enforced
by
geometric
constraints,
mechanism
investigate
using
density
functional
theory.
method
developed
here
enables
rapid
late-stage
bioactive
molecules
featuring
cyclic
linear
amines.
Overall,
general
platform
amine
constitutional
isomerization
been
achieved.
