Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(36), С. 20053 - 20061
Опубликована: Авг. 30, 2023
Small,
strained
ring
systems
are
important
pharmacophores
in
medicinal
chemistry
and
versatile
intermediates
organic
synthesis.
However,
the
kinetic
thermodynamic
instability
of
many
molecules
renders
them
challenging
to
prepare.
Here,
we
report
a
strain-inducing
positional
alkene
isomerization
reaction
that
provides
mild
selective
access
cyclobutene
building
blocks
from
readily
obtained
cyclobutylidene
precursors.
This
endergonic
relies
on
sequential
synergistic
action
decatungstate
polyanion
photocatalyst
cobaloxime
co-catalyst
store
potential
energy
form
strain.
The
versatility
products
is
demonstrated
through
diverse
subsequent
strain-releasing
transformations.
Mechanistic
studies
reveal
steric
basis
for
strain-selective
product
formation.
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.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 17, 2022
Abstract
Due
to
its
mild
reaction
conditions
and
unique
chemoselectivity,
hydrogen
atom
transfer
(HAT)
hydrogenation
represents
an
indispensable
method
for
the
synthesis
of
complex
molecules.
Its
analog
using
deuterium,
deuterium
(DAT)
deuteration,
is
expected
enable
access
deuterium‐labeled
compounds.
However,
DAT
deuteration
has
been
scarcely
studied
synthetic
purposes,
a
that
possesses
favorable
characteristics
HAT
hydrogenations
remained
elusive.
Herein,
we
report
protocol
photocatalytic
electron‐deficient
alkenes.
In
contrast
previous
this
tolerates
variety
synthetically
useful
functional
groups
including
haloarenes.
The
late‐stage
also
allows
deuterated
amino
acids
as
well
donepezil‐
d
2
.
Thus,
work
demonstrates
potential
chemistry
become
alternative
choice
preparing
deuterium‐containing
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.
