Angewandte Chemie,
Год журнала:
2023,
Номер
135(36)
Опубликована: Июль 18, 2023
Abstract
Unprotected
cis
‐2,3‐diarylpiperidines
are
synthesized
through
an
unprecedented
palladium‐catalyzed
cross‐coupling
reaction
between
aryl
halides
and
elusive
endocyclic
1‐azaallyl
anions.
These
intermediates
generated
in
situ
by
the
deprotonation
of
2‐aryl‐1‐piperideines,
precursors
that
readily
prepared
two
operations
from
simple
piperidines.
An
asymmetric
version
this
with
(2
R
,
3
)‐
i
Pr‐BI‐DIME
as
ligand
provides
products
moderate
to
good
yields
enantioselectivities.
This
study
significantly
expands
synthetic
utility
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июль 18, 2023
Unprotected
cis-2,3-diarylpiperidines
are
synthesized
through
an
unprecedented
palladium-catalyzed
cross-coupling
reaction
between
aryl
halides
and
elusive
endocyclic
1-azaallyl
anions.
These
intermediates
generated
in
situ
by
the
deprotonation
of
2-aryl-1-piperideines,
precursors
that
readily
prepared
two
operations
from
simple
piperidines.
An
asymmetric
version
this
with
(2R,
3R)-iPr-BI-DIME
as
ligand
provides
products
moderate
to
good
yields
enantioselectivities.
This
study
significantly
expands
synthetic
utility
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3653 - 3663
Опубликована: Июнь 27, 2024
Abstract
Numerous
appropriately
substituted
pyridyl
or
phenyl
groups
serve
as
a
particularly
advantageous
activation
motif
for
the
electrochemical
oxidation
of
amines.
Such
enable
general,
mild
method
α‐functionalization
tertiary
amines
across
numerous
activating
and
amine
scaffolds.
Notably,
accommodates
an
unprecedented
range
nucleophile
classes,
allowing
introduction
diverse
functional
to
readily
prepared
substrates.
The
utility
this
is
then
demonstrated
through
applications
unsymmetrical
bisfunctionalization,
site‐selective
functionalization
N
‐pyridyl
vs.
other
activated
amines,
formal
synthesis
ivosidenib
diversification
FDA‐approved
drugs
natural
product
Synthesis,
Год журнала:
2023,
Номер
55(15), С. 2343 - 2352
Опубликована: Янв. 30, 2023
Abstract
Secondary
alicyclic
amines
are
converted
into
their
corresponding
ring-fused
imidazoles
in
a
simple
procedure
consisting
of
oxidative
imine
formation
followed
by
van
Leusen
reaction.
Amines
with
an
existing
α-substituent
undergo
regioselective
ring-fusion
at
the
α′-position.
This
method
was
utilized
synthesis
fadrozole.
Organic Letters,
Год журнала:
2024,
Номер
26(28), С. 5972 - 5977
Опубликована: Июль 5, 2024
Unprotected
alicyclic
amines
undergo
α-C-H
bond
phosphonylation
via
a
two-stage
one-pot
process
involving
the
oxidation
of
amine-derived
lithium
amides
with
simple
ketone
oxidants,
generating
transient
imines
which
are
then
captured
phosphites
or
phosphine
oxides.
Amines
an
existing
α-substituent
regioselective
α'-phosphonylation.
Amine
α-arylation
and
α'-phosphonylation
can
be
combined,
difunctionalized
product
in
single
operation.
Abstract
The
prominence
of
saturated
N-heterocycle
motifs
in
pharmaceuticals
is
undeniable.
Challenges
associated
with
the
alkylation
scaffolds
to
efficiently
access
new
drug
analogues
are
hampered
by
synthetically
laborious
routes.
Stereocontrolled
alkyl-substitutions
onto
N-heterocycles
particularly
difficult
high
yields
traditional
synthetic
methods.
Alternatively,
C–H
bond
functionalization
provides
a
and
powerful
avenue
directly
selectively
functionalizing/alkylating/
arylating
abundantly
available
bonds
N-heterocycles.
This
review
highlights
complementary
methods
for
activating
functionalizing
chemo-,
regio-,
or
stereoselectively
alkylated
products.
challenge
has
required
catalyst
development
useful
N-heterocyclic
building
blocks
late-stage
functionalization.
Early
transition
metal,
late
photoredox,
electrochemical
discussed.
selective
α,
β,
γ
form
C–C,
C–N,
C–O,
C–B
presented.
1
Introduction
2
Transition
Metal
Catalyzed
α-Alkylation
3
Late
α-Functionalization
4
Photoredox-Catalyzed
5
Electrochemical
6
Functionalization
β
Bonds
7
Conclusions/Outlook
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
Heterogeneous
visible
light
photocatalysis
is
a
compelling
approach
to
address
sustainability
in
synthetic
photochemistry.
However,
the
use
of
solid‐state
photocatalysts
remains
very
unpopular
organic
synthesis
because
their
limited
accessibility
and
black‐box
effect
associated
lack
rational
between
molecular
structure
photochemical
properties.
Herein,
we
disclose
synthesis,
characterization,
photocatalytic
properties
applications
simple
readily
available
conjugated
polymer,
poly‐(
para
‐phenylene
ethynylene)
1
,
which
exhibits
strong
oxidative
power
upon
irradiation
with
(E(
1*
/
⋅
−
)=+1.67
V
vs
SCE).
Comparisons
structural
analogues
highlighted
superior
activity
this
linear
semiconductor,
on
account
its
fully
architecture.
The
excited‐state
reactivity
enabled
transformation
various
amines
into
imines
batch
continuous
flow
reactors
together
straightforward
photocatalyst
recycling.
Mechanistic
investigations
revealed
concomitant
photoredox
energy
transfer
pathways,
that
led
formation
desired
products.
Ultimately,
inline
generation
was
exploited
telescoped
three‐component
Ugi
reactions
(3CR)
toward
biologically
relevant
α‐acylaminoamides.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
Heterogeneous
visible
light
photocatalysis
is
a
compelling
approach
to
address
sustainability
in
synthetic
photochemistry.
However,
the
use
of
solid‐state
photocatalysts
remains
very
unpopular
organic
synthesis
because
their
limited
accessibility
and
black‐box
effect
associated
lack
rational
between
molecular
structure
photochemical
properties.
Herein,
we
disclose
synthesis,
characterization,
photocatalytic
properties
applications
simple
readily
available
conjugated
polymer,
poly‐(
para
‐phenylene
ethynylene)
1
,
which
exhibits
strong
oxidative
power
upon
irradiation
with
(E(
1*
/
⋅
−
)=+1.67
V
vs
SCE).
Comparisons
structural
analogues
highlighted
superior
activity
this
linear
semiconductor,
on
account
its
fully
architecture.
The
excited‐state
reactivity
enabled
transformation
various
amines
into
imines
batch
continuous
flow
reactors
together
straightforward
photocatalyst
recycling.
Mechanistic
investigations
revealed
concomitant
photoredox
energy
transfer
pathways,
that
led
formation
desired
products.
Ultimately,
inline
generation
was
exploited
telescoped
three‐component
Ugi
reactions
(3CR)
toward
biologically
relevant
α‐acylaminoamides.
