Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(16), P. 2934 - 2938
Published: April 14, 2023
Herein,
we
report
the
gold-catalyzed
aryl-alkenylation
of
unactivated
alkenes
with
alkenyl
iodides
and
bromides
employing
ligand-enabled
gold
redox
catalysis.
The
present
methodology
followed
π-activation
pathway
rather
than
migratory
insertion
pathway,
which
is
predominant
in
other
transition
metal
catalysis
such
as
Pd,
Ni,
Cu,
etc.
Detailed
mechanistic
investigations
31P
NMR,
deuterium
labeling,
HRMS
studies
have
been
carried
out
to
underpin
insights.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7089 - 7095
Published: April 18, 2022
Presented
herein
is
the
first
report
of
enantioselective
Au(I)/Au(III)
redox
catalysis,
enabled
by
a
newly
designed
hemilabile
chiral
(P,N)-ligand
(ChetPhos).
The
potential
this
concept
has
been
demonstrated
development
1,2-oxyarylation
and
1,2-aminoarylation
alkenes
which
provided
direct
access
to
medicinally
relevant
3-oxy-
3-aminochromans
(up
88%
yield
99%
ee).
DFT
studies
were
carried
out
unravel
enantiodetermining
step,
revealed
that
stronger
trans
influence
phosphorus
allows
selective
positioning
substrate
in
C2-symmetric
environment
present
around
nitrogen,
imparting
high
level
enantioselectivity.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(17), P. 7358 - 7426
Published: Jan. 1, 2022
Transition
metal
catalysis
has
contributed
immensely
to
C-C
bond
formation
reactions
over
the
last
few
decades,
and
alkylation
is
no
exception.
The
superiority
of
such
methodologies
traditional
evident
from
minimal
reaction
steps,
shorter
times,
atom
economy
while
also
allowing
control
regio-
stereo-selectivity.
In
particular,
hydrocarbonation
alkenes
grabbed
increased
attention
due
its
fundamental
ability
effectively
selectively
synthesise
a
wide
range
industrially
pharmaceutically
relevant
moieties.
This
review
attempts
provide
scientific
viewpoint
systematic
analysis
recent
developments
in
transition-metal-catalyzed
various
C-H
bonds
using
simple
activated
olefins.
key
features
mechanistic
studies
involved
these
transformations
are
described
briefly.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(16), P. 8810 - 8816
Published: April 16, 2023
Herein,
we
report
a
gold-catalyzed
Heck
reaction
facilitated
by
the
ligand-enabled
Au(I)/Au(III)
redox
catalysis.
The
elementary
organometallic
steps
such
as
migratory
insertion
and
β-hydride
elimination
have
been
realized
in
catalytic
fashion
for
first
time
gold
chemistry.
present
methodology
not
only
overcomes
limitations
of
previously
known
transition
metal-catalyzed
reactions
requirement
specialized
substrates
formation
mixture
regioisomeric
products
result
undesirable
chain-walking
process
but
also
offers
complementary
regioselectivity
compared
to
other
metal
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 4142 - 4149
Published: Feb. 8, 2023
Alkene
functionalization
with
a
single-atom
catalyst
(SAC)
which
merges
homogeneous
and
heterogeneous
catalysis
is
fascinating
route
to
obtain
high-value-added
molecules.
However,
C–N
bond
formation
of
alkene
SAC
still
unexplored.
Herein,
bimetal-organic
framework-derived
Co–N/C
an
atomically
dispersed
cobalt
center
reported
show
good
activity
chemoselective
aziridination/oxyamination
reactions
from
hydroxylamine,
late-stage
complex
alkenes
diversified
synthetic
transformations
the
aziridine
product
further
expand
utility
this
method.
Moreover,
system
proceeds
without
external
oxidants
exhibits
mild,
atom-economic,
recyclable
characters.
Detailed
spectroscopic
characterizations
mechanistic
studies
revealed
structure
catalytic
possible
intermediates
involved
in
mechanism
cycle.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(27)
Published: April 30, 2024
Abstract
In
this
minireview
we
survey
the
challenges
and
strategies
in
gold
redox
catalysis.
Gold's
reluctance
to
oxidative
addition
reactions
due
its
high
potential
limits
applicability.
Initial
attempts
overcome
problem
focused
on
use
of
sacrificial
external
oxidants
stoichiometric
amounts
bring
Au(I)
compounds
Au(III)
reactive
species.
Recently,
innovative
approaches
employing
hemilabile
ligands,
which
are
capable
coordinating
stabilizing
square‐planar
intermediates,
thus
facilitating
steps
enabling
oxidant‐free
Notable
examples
include
(P^N)
bidendate
MeDalphos
ligand
achieve
various
cross‐coupling
via
Au(I)/Au(III).
Importantly,
ligand‐enabled
catalysis
allows
merging
with
π‐activation,
such
as
oxy‐
aminoarylation
alkenols
alkenamines
using
organohalides,
expanding
gold‘s
versatility
C−C
C‐heteroatom
bond
formations
unprecedented
cyclizations.
Moreover,
recent
advancements
enantioselective
chiral
ligands
also
surveyed.
Strikingly,
versatile
bidentate
(C^N)
competitors
have
appeared
recently,
by
designing
scaffolds
where
phosphine
groups
substituted
N‐heterocyclic
or
mesoionic
carbenes.
Overall,
these
highlight
evolving
landscape
tremendous
a
broad
scope
transformations.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 17, 2025
Direct
synthesis
of
enantioenriched
scaffolds
with
multiple
adjacent
stereocenters
remains
an
important
yet
challenging
task.
Herein,
we
describe
a
highly
diastereo-
and
enantioselective
Cu-catalyzed
alkylboration
cyclopropenes,
less
reactive
alkyl
iodides
as
electrophiles,
for
the
efficient
tetra-substituted
borylated
cyclopropanes
bearing
three
consecutive
stereocenters.
This
protocol
features
mild
conditions,
broad
substrate
scope,
good
functional
group
tolerance,
affording
array
chiral
in
to
high
yields
excellent
enantioselectivities.
Detailed
mechanistic
experiments
kinetic
studies
were
conducted
elucidate
reaction
pathway
rate-determining
step
reaction.
DFT
calculations
revealed
that
π···π
stacking
interaction
between
phenyl
groups
on
phosphorus
ligand,
along
smaller
distortion
CuL-Bpin
part,
contributed
The
synthetic
utility
was
showcased
by
facile
some
valuable
centers.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
144(1), P. 339 - 348
Published: Dec. 22, 2021
A
copper-catalyzed
remote
benzylic
C-H
functionalization
strategy
enabling
1,2-difunctionalization
of
alkenes
with
2-methylbenzeneamides
and
nucleophiles,
including
alcohols,
indoles,
pyrroles,
the
intrinsic
amino
groups,
is
reported,
which
characterized
by
its
redox-neutral
conditions,
exquisite
site-selectivity,
broad
substrate
scope,
wide
utilizations
late-stage
modifying
bioactive
molecules.
This
reaction
proceeds
through
nitrogen-centered
radical
generation,
hydrogen
atom
transfer,
addition
across
alkenes,
single-electron
oxidation,
carbocation
electrophilic
course
cascades.
While
using
external
nucleophiles
manipulates
three-component
alkene
alkylalkoxylation
alkyl-heteroarylation
to
access
dialkyl
ethers,
3-alkylindoles,
3-alkylpyrroles,
omitting
results
in
two-component
alkylamidation
([5+2]
annulation)
benzo-[f][1,2]thiazepine
1,1-dioxides.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(34)
Published: April 14, 2022
Enantioselective,
intermolecular
alkene
arylamination
was
achieved
through
gold
redox
catalysis.
Screening
of
ligands
revealed
chiral
P,N
as
the
optimal
choice,
giving
aminoarylation
with
good
yields
(up
to
80
%)
and
excellent
stereoselectivity
99
:
1
er).
As
first
example
enantioselective
catalysis,
this
work
confirmed
feasibility
applying
a
ligand
at
gold(I)
stage,
stereodetermining
step
(SDS)
gold(III)
intermediate,
thus
opening
up
new
way
conduct
catalysis
stereochemistry
control.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(2), P. 993 - 1003
Published: Jan. 3, 2022
A
(MeDalphos)AuCl
complex
was
found
to
efficiently
catalyze
the
cross-coupling
of
indoles
and
allyl
acetates/alcohols.
The
reaction
tolerates
many
functional
groups
selectively
affords
branched
C3-allylated
products
from
both
α-
γ-substituted
substrates.
It
takes
advantage
hemilabile
character
P∧N
ligand.
C(sp2)–C(sp3)
coupling
operates
via
a
Au(I)/Au(III)
redox
cycle
involves
dicationic
π-allyl
Au(III)
as
key
intermediate.
In
this
case,
moiety
adopts
an
asymmetric
σ
+
π-coordination
mode,
substantiated
by
NMR
spectroscopy
density
theory
(DFT)
calculations.