Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(32), P. 6819 - 6824
Published: Aug. 6, 2024
With
alanine
as
a
transient
directing
group,
Pd-catalyzed
regioselective
alkynylation
at
the
indole
C4-position
was
successfully
established
in
good
yield.
The
total
synthesis
of
PAF
antagonist
demonstrated
synthetic
utility
this
protocol.
regioselectivity
explicitly
proven
by
prepared
C4-selective
palladacycle
intermediate
catalytic
process
and
DFT
calculation
energy
barriers
C4-
C2-site-selective
C-H
activation
indole.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(19)
Published: Feb. 29, 2024
Abstract
In
2001,
our
curiosity
to
understand
the
stereochemistry
of
C−H
metalation
with
Pd
prompted
first
studies
in
Pd(II)‐catalyzed
asymmetric
activation
(RSC
Research
appointment:
020
7451
2545,
Grant:
RG
36873,
Dec.
2002).
We
identified
four
central
challenges:
1.
poor
reactivity
simple
salts
native
substrates;
2.
few
strategies
control
site
selectivity
for
remote
bonds;
3.
lack
chiral
catalysts
achieve
enantioselectivity
via
metalation,
and
4.
low
practicality
due
limited
coupling
partner
scope
use
specialized
oxidants.
These
challenges
necessitated
new
catalyst
reaction
development.
For
,
we
developed
approaches
enhance
substrate–catalyst
affinity
together
novel
bifunctional
ligands
which
participate
accelerate
cleavage
step.
site‐selectivity
introduced
concept
systematically
modulating
distance
geometry
between
a
directing
template,
catalyst,
substrate
selectively
access
bonds.
devised
predictable
stereomodels
catalyst‐controlled
enantioselective
based
on
participation
ligands.
Finally,
have
varied
catalytic
manifolds
Pd(II)
accommodate
diverse
partners
while
employing
practical
oxidants
such
as
peroxides.
advances
culminated
numerous
reactions,
setting
stage
broad
industrial
applications.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
Differentiating
between
two
highly
similar
C-H
bonds
in
a
given
molecule
remains
fundamental
challenge
synthetic
organic
chemistry.
Directing
group
assisted
strategies
for
the
functionalisation
of
proximal
has
been
known
last
few
decades.
However,
distal
bond
is
strenuous
and
requires
distinctly
specialised
techniques.
In
this
review,
we
summarise
advancement
Pd-catalysed
C(sp
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 19, 2024
Abstract
Aliphatic
allylic
amines
are
common
in
natural
products
and
pharmaceuticals.
The
oxidative
intermolecular
amination
of
C(sp
3
)-H
bonds
represents
one
the
most
straightforward
strategies
to
construct
these
motifs.
However,
utilization
widely
internal
alkenes
with
this
transformation
remains
a
synthetic
challenge
due
inefficient
coordination
metals
excessive
aliphatic
aromatic
amines,
resulting
decreasing
reactivity
catalyst.
Here,
we
present
regioselective
Cu-catalyzed
olefins
azodiformates
problems.
A
removable
bidentate
directing
group
is
used
control
regiochemistry
stabilize
π-allyl-metal
intermediate.
Noteworthy
dual
role
as
both
nitrogen
source
an
electrophilic
oxidant
for
C-H
activation.
This
protocol
features
simple
conditions,
remarkable
scope
functional
tolerance
evidenced
by
>40
examples
exhibits
high
regioselectivity
excellent
E/Z
selectivity.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(48)
Published: Aug. 7, 2024
Abstract
Deuterated
and
tritiated
analogs
of
drugs
are
valuable
compounds
for
pharmaceutical
medicinal
chemistry.
In
this
work,
we
present
a
novel
hydrogen
isotope
exchange
reaction
using
non‐directed
homogeneous
Pd‐catalysis.
Aromatic
C−H
activation
is
achieved
by
commercially
available
pyridine
ligand.
Using
the
most
convenient
cheapest
deuterium
source,
D
2
O,
as
only
solvent
39
pharmaceuticals
were
labelled
with
clean
profiles
high
uptakes.
Additionally,
describe
first
application
Pd‐catalysis
H/T
on
three
different
T
O
isotopic
demonstrating
applicability
to
synthesis
radiotracers.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(45), P. 20550 - 20553
Published: Nov. 7, 2022
Ligand
development
has
enabled
rapid
advances
in
Pd(II)-catalyzed
β-methyl
C(sp3)–H
activation
of
free
carboxylic
acids.
However,
there
are
only
a
handful
reports
free-acid-directed
β-methylene
activation,
all
which
limited
to
intramolecular
reactions.
Herein,
we
report
the
first
intermolecular
arylation
aliphatic
acids,
is
by
bidentate
pyridine–pyridone
ligands.
The
bite
angle
this
ligand
been
discovered
play
key
role
promoting
C–H
acid.
This
new
transformation
provides
disconnection
for
alkylation
arenes
with
simple
A
variety
including
antiasthmatic
drug
seratrodast,
were
compatible
reported
protocol.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: June 3, 2022
α-C-H-functionalization
of
ketones
and
aldehydes
has
been
intensively
explored
in
organic
synthesis.
The
functionalization
unactivated
β-C-H
bonds
such
carbonyl
compounds
is
less
well
investigated
developing
a
general
method
for
their
arylation
remains
challenging.
Herein
we
report
that
uses
cooperative
nickel
photoredox
catalysis
the
formal
with
(hetero)aryl
bromides.
features
mild
conditions,
remarkable
scope
wide
functional
group
tolerance.
Importantly,
introduced
synthetic
strategy
also
allows
β-alkenylation,
β-alkynylation
β-acylation
under
similar
conditions.
Mechanistic
studies
revealed
this
transformation
proceeds
through
single
electron
oxidation/Ni-mediated
coupling/reductive
elimination
cascade.
