Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
Abstract
Oxetanes
are
valuable
motifs
in
medicinal
chemistry
applications,
with
demonstrated
potential
to
serve
as
bioisosteres
for
an
array
of
functional
groups.
Through
the
visible‐light‐mediated
photoredox
hydrodecarboxylation
2‐aryl
oxetane
2‐carboxylic
acids
this
work
enables
access
products
a
[2+2]‐photocycloaddition
between
alkenes
and
aryl
aldehydes
without
challenges
associated
traditional
UV‐light‐mediated
Paternò‐Büchi
reaction.
Investigation
into
mechanism
reveals
substrate‐dependent
modes
initiation
under
conditions
reported
herein.
Divergence
diastereomeric
outcome
is
observed,
mechanistic
probes
elucidating
key
hydrogen‐bonding
steric
interactions.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(9), С. 6209 - 6216
Опубликована: Фев. 22, 2024
Chiral
aminoalcohols
are
omnipresent
in
bioactive
compounds.
Conventional
strategies
to
access
this
motif
involve
multiple-step
reactions
install
the
requisite
functionalities
stereoselectively
using
conventional
polar
bond
analysis.
This
study
reveals
that
a
simple
chiral
oxazolidine-based
carboxylic
acid
can
be
readily
transformed
substituted
with
high
stereochemical
control
by
Ni-electrocatalytic
decarboxylative
arylation.
general,
robust,
and
scalable
coupling
used
synthesize
variety
of
medicinally
important
compounds,
avoiding
protecting
functional
group
manipulations,
thereby
dramatically
simplifying
their
preparation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(37), С. 25780 - 25787
Опубликована: Сен. 5, 2024
Carboxylic
acids
and
their
derivatives
are
powerful
building
blocks
in
dual
Ir/Ni
metallaphotoredox
methods
of
decarboxylative
arylation
due
to
abundance
as
feedstock
compounds.
However,
the
library
accessible
carboxylic
is
limited
by
trends
radical
stability,
often
necessitating
development
specific
systems
for
challenging
substrates.
Herein,
we
disclose
application
a
new
Ir(III)
photocatalyst
low-energy
orange
light
system
with
broad
applicability
activating
both
native
redox-active
esters
(RAEs).
This
method
represents
first
known
example
complementary
oxidative
reductive
paradigms
broadly
similar
reaction
conditions,
unlocking
reactivity
We
further
show
wide
scope
aryl
halide
acid
coupling
partners
regimes,
added
advantages
over
blue-light-catalyzed
alkylation
photosensitive
ACS Catalysis,
Год журнала:
2023,
Номер
13(18), С. 11910 - 11918
Опубликована: Авг. 25, 2023
Dual
nickel
photoredox
catalysis
conditions
have
been
developed
for
the
decarboxylative
cross-coupling
of
aryl
halides
and
carboxylic
acids
containing
fully
substituted
α-carbons,
a
valuable
but
challenging
substrate
class
C(sp2)–C(sp3)
bond-forming
reactions.
High-throughput
experimentation
identified
Ni(TMHD)2
as
optimal
precatalyst
this
reaction
in
contrast
to
nickel-bipyridyl
complexes
typically
employed
couplings,
which
predominantly
furnished
undesired
C–O
products.
Computational
work
provides
insight
into
potential
mechanistic
underpinnings
C–C
vs
selectivity
nickel-diketonate
complex.
Morpholines
are
common
heterocycles
in
pharmaceutical
and
agricultural
products,
yet
methods
to
synthesize
them
from
1,2-amino
alcohols
inefficient.
We
report
the
simple,
high
yielding,
one
or
two-step,
redox
neutral
protocol
using
inexpensive
reagents
(ethylene
sulfate
tBuOK)
for
conversion
of
morpholines.
Key
this
methodology
is
identification
general
conditions
that
allow
clean
isolation
monoalkylation
products
derived
a
simple
SN2
reaction
between
an
amine
ethylene
sulfate.
Experiments
suggest
degree
selectivity
dependent
upon
structure
reacting
alcohol
as
well
unique
properties
This
method
can
be
used
synthesis
variety
morpholines
containing
substituents
at
various
positions,
including
28
examples
primary
amines
multiple
contained
known
active
ingredients.
have
conducted
on
>50
g
scale.
also
demonstrated
formal
morpholine
Overall,
while
new
has
many
environmental
safety
benefits
relative
traditional
prepare
most
striking
feature
facile
selective
amines.
explored
reactions
beyond
those
related
morpholines,
obtaining
proof-of-principle
piperazines
2-carbon
electrophile
fragment
couplings.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 17, 2024
Morpholines
are
common
heterocycles
in
pharmaceutical
and
agricultural
products,
yet
methods
to
synthesize
them
from
1,2-amino
alcohols
inefficient.
We
report
the
simple,
high
yielding,
one
or
two-step,
redox
neutral
protocol
using
inexpensive
reagents
(ethylene
sulfate
Dual
nickel
photoredox
catalysis
conditions
have
been
developed
for
the
decarboxylative
cross-coupling
of
aryl
halides
and
carboxylic
acids
containing
fully
substituted
alpha
carbons,
a
valuable
but
challenging
substrate
class
C(sp2)–C(sp3)
bond-forming
reactions.
High-throughput
experimentation
identified
Ni(TMHD)2
as
optimal
precatalyst
this
reaction
in
contrast
to
nickel-bipyridyl
complexes
typically
employed
couplings,
which
predominantly
furnished
undesired
C–O
products.
Computational
work
provides
insight
into
potential
mechanistic
underpinnings
C–C
vs.
selectivity
nickel-diketonate
complex.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 29, 2024
Abstract
The
development
of
robust
and
reliable
methods
for
the
construction
C(sp
2
)−C(sp
3
)
bonds
is
vital
accessing
an
increased
array
structurally
diverse
scaffolds
in
drug
discovery
campaigns.
While
significant
advances
towards
this
goal
have
been
achieved
using
metallaphotoredox
chemistry,
many
these
utilise
photocatalysts
based
on
precious‐metals
due
to
their
efficient
redox
processes
tuneable
properties.
However,
cost,
scarcity,
toxicity
metals,
search
suitable
replacements
should
be
a
priority.
Here,
we
show
use
commercially
available
heterogeneous
semiconductor
graphitic
carbon
nitride
(gCN)
as
photocatalyst,
combined
with
nickel
catalysis,
cross‐coupling
between
aryl
halide
carboxylic
acid
coupling
partners.
gCN
has
shown
engage
single‐electron‐transfer
(SET)
energy‐transfer
(EnT)
formation
C−X
bonds,
manuscript
overcome
previous
limitations
furnish
C−C
over
C−O
acids.
A
broad
scope
both
halides
acids
presented,
recycling
photocatalyst
demonstrated.
mechanism
reaction
also
investigated.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
Abstract
Oxetanes
are
valuable
motifs
in
medicinal
chemistry
applications,
with
demonstrated
potential
to
serve
as
bioisosteres
for
an
array
of
functional
groups.
Through
the
visible‐light‐mediated
photoredox
hydrodecarboxylation
2‐aryl
oxetane
2‐carboxylic
acids
this
work
enables
access
products
a
[2+2]‐photocycloaddition
between
alkenes
and
aryl
aldehydes
without
challenges
associated
traditional
UV‐light‐mediated
Paternò‐Büchi
reaction.
Investigation
into
mechanism
reveals
substrate‐dependent
modes
initiation
under
conditions
reported
herein.
Divergence
diastereomeric
outcome
is
observed,
mechanistic
probes
elucidating
key
hydrogen‐bonding
steric
interactions.
