Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16330 - 16336
Опубликована: Июль 20, 2023
Quaternary
carbons
are
ubiquitous
in
bioactive
molecules;
however,
synthetic
methods
for
the
construction
of
this
motif
remain
underdeveloped.
Here,
we
report
synthesis
quaternary
from
tertiary
alcohols,
a
class
structurally
diverse,
bench-stable
feedstocks,
via
merger
photoredox
catalysis
and
iron-mediated
SH2
bond
formation.
This
alcohol-bromide
cross-coupling
is
enabled
by
novel
halogen-atom
transfer
(XAT)
reagent,
which
first
reductively
activated
XAT
reagent
to
be
reported.
A
wide
variety
sterically
congested
products
can
accessed
through
mild
practical
protocol
including
derived
both
alkylation
benzylation
fragments.
We
further
demonstrate
utility
method
expedited
liver
receptor
agonist
two-step
conversion
ketones
esters
products,
enables
modular
control
up
three
four
substituents
on
center.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(29), С. 10882 - 10889
Опубликована: Июль 13, 2021
We
describe
a
photocatalytic
system
that
elicits
potent
photoreductant
activity
from
conventional
photocatalysts
by
leveraging
radical
anion
intermediates
generated
in
situ.
The
combination
of
an
isophthalonitrile
photocatalyst
and
sodium
formate
promotes
diverse
aryl
coupling
reactions
abundant
but
difficult
to
reduce
chloride
substrates.
Mechanistic
studies
reveal
two
parallel
pathways
for
substrate
reduction
both
enabled
key
terminal
reductant
byproduct,
carbon
dioxide
anion.
Mechanochemical
transformations
have
made
chemists
enter
unknown
territories,
forcing
a
different
chemistry
perspective.
While
questioning
or
revisiting
familiar
concepts
belonging
to
solution
chemistry,
mechanochemistry
has
broken
new
ground,
especially
in
the
panorama
of
organic
synthesis.
Not
only
does
it
foster
"thinking
outside
box",
but
also
opened
reaction
paths,
allowing
overcome
weaknesses
traditional
exactly
where
use
well-established
solution-based
methodologies
rules
out
progress.
In
this
Review,
reader
is
introduced
an
intriguing
research
subject
not
yet
fully
explored
and
waiting
for
improved
understanding.
Indeed,
study
mainly
focused
on
that,
although
impossible
solution,
become
possible
under
mechanochemical
processing
conditions,
simultaneously
entailing
innovation
expanding
chemical
space.
Science,
Год журнала:
2023,
Номер
380(6640), С. 81 - 87
Опубликована: Апрель 6, 2023
The
Kolbe
reaction
forms
carbon-carbon
bonds
through
electrochemical
decarboxylative
coupling.
Despite
more
than
a
century
of
study,
the
has
seen
limited
applications
owing
to
extremely
poor
chemoselectivity
and
reliance
on
precious
metal
electrodes.
In
this
work,
we
present
simple
solution
long-standing
challenge:
Switching
potential
waveform
from
classical
direct
current
rapid
alternating
polarity
renders
various
functional
groups
compatible
enables
sustainable
carbon-based
electrodes
(amorphous
carbon).
This
breakthrough
enabled
access
valuable
molecules
that
range
useful
unnatural
amino
acids
promising
polymer
building
blocks
readily
available
carboxylic
acids,
including
biomass-derived
acids.
Preliminary
mechanistic
studies
implicate
role
in
modulating
local
pH
around
crucial
acetone
as
an
unconventional
solvent
for
reaction.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(24), С. 13609 - 13613
Опубликована: Апрель 9, 2021
We
report
a
late-stage
heteroarylation
of
aryl
sulfonium
salts
through
activation
with
α-amino
alkyl
radicals
in
mechanistically
distinct
approach
from
previously
reported
halogen-atom
transfer
(XAT).
The
new
mode
proceeds
the
absence
light
and
photoredox
catalysts,
engaging
wide
range
hetarenes.
Furthermore,
we
demonstrate
applicability
this
methodology
synthetically
useful
cross-coupling
transformations.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(15), С. 6291 - 6306
Опубликована: Янв. 1, 2022
This
review
is
a
systematic
summary
of
radical
deuteration
with
four
reaction
types:
reductive
deuteration,
defunctionalization–deuteration,
hydrogen–deuterium
(H/D)
exchange
and
deuteroalkylation.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(4), С. 1986 - 1992
Опубликована: Янв. 21, 2022
We
report
here
a
mechanistically
distinct
approach
to
achieve
Suzuki-Miyaura-type
cross-couplings
between
alkyl
iodides
and
aryl
organoborons.
This
process
requires
copper
catalyst
but,
in
contrast
with
previous
approaches
based
on
palladium
nickel
systems,
does
not
utilizes
the
metal
for
activation
of
electrophile.
Instead,
this
strategy
exploits
halogen-atom-transfer
ability
α-aminoalkyl
radicals
convert
secondary
into
corresponding
that
then
are
coupled
aryl,
vinyl,
alkynyl,
benzyl,
allyl
boronate
species.
These
novel
coupling
reactions
feature
simple
setup
conditions
(1
h
at
room
temperature)
facilitate
access
privileged
motifs
targeted
by
pharmaceutical
sector.
