Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(34), P. 18939 - 18947
Published: Aug. 16, 2023
Aminoboration
of
simple
alkenes
with
nitrogen
nucleophiles
remains
an
unsolved
problem
in
synthetic
chemistry;
this
transformation
can
be
catalyzed
by
palladium
via
aminopalladation
followed
transmetalation
a
diboron
reagent.
However,
catalytic
process
faces
inherent
challenges
instability
the
alkylpalladium(II)
intermediate
toward
β-hydride
elimination.
Herein,
we
report
palladium/iron
cocatalyzed
aminoboration,
which
enables
transformation.
We
demonstrate
these
conditions
on
variety
and
norbornenes
array
common
nucleophiles.
In
developed
strategy,
iron
cocatalyst
is
crucial
to
achieving
desired
reactivity
serving
as
halophilic
Lewis
acid
release
transmetalation-active
cationic
alkylpalladium
intermediate.
Furthermore,
it
serves
redox
shuttle
regeneration
Pd(II)
catalyst
reactivation
nanoparticulate
palladium.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 10142 - 10149
Published: March 27, 2024
Saturated
bicyclic
compounds
make
up
a
valuable
class
of
building
blocks
in
the
development
agrochemicals
and
pharmaceuticals.
Here,
we
present
synthesis
borylated
bicyclo[2.1.1]hexanes
via
crossed
[2
+
2]-cycloaddition.
Due
to
presence
C–B
bond,
variety
structures
can
be
easily
prepared
that
are
not
accessible
by
other
methods.
Moreover,
rare
photo-ene
reaction
is
also
disclosed,
allowing
for
diastereoselective
trisubstituted
cyclopentanes.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 25, 2022
Regiodivergent
alkene
functionalization
that
produces
either
regioisomer
starting
from
the
same
raw
materials
is
desirable.
Herein,
we
report
a
nickel-catalyzed
switchable
site-selective
hydroalkylation.
The
selection
of
reaction
temperatures
leads
to
protocols
provide
regiodivergent
hydroalkylated
products
single
substrate.
This
protocol
allows
convenient
synthesis
α-
and
β-branched
protected
amines,
both
which
are
important
fields
pharmaceutical
chemistry
biochemistry.
In
addition,
enantioenriched
alkylamines
can
be
accessed
in
catalytic
asymmetric
variant.
Preliminary
mechanistic
studies
indicate
formation
more
stable
nickelacycle
provides
driving
force
migration.
thermodynamic
kinetic
properties
different
reduction
elimination
intermediates
responsible
for
site-selectivity.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(32)
Published: May 24, 2024
Abstract
Radical‐involved
multicomponent
difunctionalization
of
1,3‐dienes
has
recently
emerged
as
a
promising
strategy
for
rapid
synthesis
valuable
allylic
compounds
in
one‐pot
operation.
However,
the
expansion
radical
scope
and
enantiocontrol
remain
two
major
challenges.
Herein,
we
describe
an
unprecedented
photoinduced
copper‐catalyzed
highly
enantioselective
three‐component
1,2‐azidooxygenation
with
readily
available
azidobenziodazolone
reagent
carboxylic
acids.
This
mild
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
exceptional
control
over
chemo‐,
regio‐
enantioselectivity,
providing
practical
access
to
diverse
azidated
chiral
esters.
Mechanistic
studies
imply
that
copper
complex
is
implicated
bifunctional
catalyst
both
photoredox
catalyzed
azidyl
generation
C−O
cross‐coupling.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(25), P. 17140 - 17149
Published: June 12, 2024
Enantioselective
three-component
difunctionalization
of
alkenes
with
boron
reagents
represents
an
attractive
strategy
for
assembling
three-dimensional
chiral
organoboron
compounds.
However,
regio-
and
enantiocontrol
comprise
the
pivot
challenges
in
these
transformations,
which
predominantly
require
use
activated
conjugated
alkenes.
Herein,
by
utilizing
various
carbonyl
directing
groups,
including
amides,
sulfinamides,
ketones,
esters,
we
succeed
realizing
a
nickel-catalyzed
1,2-borylalkynylation
unactivated
to
enable
simultaneous
incorporation
entity
sp-fragment
across
double
bond.
The
products
contain
boryl,
alkynyl,
functional
groups
orthogonal
synthetic
reactivities,
offering
three
handles
further
derivatization
access
valuable
intermediates.
utility
this
ligand-enabled
asymmetric
protocol
has
been
highlighted
through
late-stage
decoration
drug-relevant
molecules.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 18866 - 18872
Published: July 5, 2024
C-Glycosides
are
important
structures
that
common
to
natural
products
and
pharmaceutical
agents.
Established
methods
for
their
synthesis
involve
the
reaction
of
an
activated
anomeric
carbon.
In
this
study,
we
report
a
conceptually
new
approach
involves
stereoselective
Ni-catalyzed
carboboration
glycals.
these
reactions,
not
only
is
C–C
bond
formed
at
carbon,
but
synthetically
useful
C–B
also
installed.
Upon
oxidation,
differentially
protected
C-glycosides
be
formed.
addition,
stereospecific
manipulation
leads
diverse
C-glycosides.
Finally,
application
method
in
established
C-glycosides,
such
as
C-glycosyl
amino
acids,
well
strategy
make
all
possible
diastereomers
C1
C2.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(15), P. 11318 - 11331
Published: July 15, 2024
Catalytic
enantioselective
borylation
reactions
of
unsaturated
bonds
as
powerful
tools
for
the
synthesis
diverse
chiral
organoboron
compounds
have
gained
much
attention
and
wide
applications
in
various
fields.
However,
atroposelective
arylboration
reaction
with
carbon–carbon
triple
1,3-enynes
to
obtain
axially
1,3-dienylboronates
remains
an
elusive
significant
challenge.
Hence,
we
develop
a
cooperative
copper-
palladium-catalyzed
assemble
plentiful
function
enriched
single
step
from
easily
available
1,3-enynes,
B2pin2,
aryl
bromides
high
levels
chemo-,
regio-,
stereo-,
atroposelectivity.
The
mild
conditions
lead
good
functional
group
tolerance,
which
is
proven
by
broad
substrate
scope
late-stage
functionalizations
bioactive
or
drug
molecules.
Moreover,
can
be
scaled
up,
series
further
transformations
achieved.
It
worth
emphasizing
that
several
olefin
catalysts
ligands
axial
chirality
also
synthesized
through
corresponding
elaborations
such
products,
explains
transformative
ability
application
potential
1,3-dienylboronates.
mechanism
experiment
density
theory
(DFT)
calculations
revealed
process
copper
palladium
catalysis,
indicating
chemoselectivity
regioselectivity
boration
are
determined
enyne
insertion
on
copper,
atroposelectivity
controlled
reductive
elimination
center.
Meanwhile,
calculation
demonstrated
distinct
interactions
between
P═O
C═O
groups
Pd
Bpin
center
key
transition
state
formation
products
varying
configurations
while
employing
identical
configuration
ligands.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
multiligand-involved
Cu
catalysis
offers
an
efficient
Hiyama
coupling
of
arylsilanes
with
unactivated
alkyl
halides,
where
copper
NHC
and
phenanthroline
ligands
were
account
for
C(sp
2
)–Si
activation
)–C(sp
3
)
formation,
respectively.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(46)
Published: Oct. 17, 2022
Two
catalytic
systems
have
been
developed
for
the
arylboration
of
endocyclic
enecarbamates
to
deliver
synthetically
versatile
borylated
saturated
N-heterocycles
in
good
regio-
and
diastereoselectivities.
A
Cu/Pd
dual
reaction
enables
synthesis
borylated,
α-arylated
azetidines,
while
a
Ni-catalysed
efficiently
functionalizes
5-,
6-,
7-membered
enecarbamates.
In
case
Cu/Pd-system,
remarkable
additive
effect
was
identified
that
allowed
broader
scope.
The
products
are
useful,
as
demonstrated
by
manipulations
boronic
ester
access
biologically
active
compounds.
