Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(23), P. 3360 - 3372
Published: Jan. 1, 2023
This
feature
article
outlines
the
up-to-date
implementation
of
anion-binding
catalysis
for
enantioselective
dearomatization
hereoarenes,
expanding
chemical
space
by
converting
available
flat
building
blocks
into
valuable
chiral
molecules.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(12), P. 7692 - 7760
Published: May 10, 2023
Site-predictable
and
chemoselective
C–H
bond
functionalization
reactions
offer
synthetically
powerful
strategies
for
the
step-economic
diversification
of
both
feedstock
fine
chemicals.
Many
transition-metal-catalyzed
methods
have
emerged
selective
activation
bonds.
However,
challenges
regio-
chemoselectivity
with
application
to
highly
complex
molecules
bearing
significant
functional
group
density
diversity.
As
molecular
complexity
increases
within
structures
risks
catalyst
intolerance
limited
applicability
grow
number
groups
potentially
Lewis
basic
heteroatoms.
Given
abundance
bonds
already
diversified
such
as
pharmaceuticals,
natural
products,
materials,
design
selection
reaction
conditions
tolerant
catalysts
has
proved
critical
successful
direct
functionalization.
such,
innovations
formation
carbon–carbon
been
discovered
developed
overcome
these
limitations.
This
review
highlights
progress
made
metal-catalyzed
C–C
forming
including
alkylation,
methylation,
arylation,
olefination
targets.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(12), P. 5042 - 5100
Published: Jan. 1, 2022
Transition
metal-catalysed
direct
borylation
of
hydrocarbons
via
C–H
bond
activation
has
received
a
remarkable
level
attention
as
popular
reaction
in
the
synthesis
organoboron
compounds
owing
to
their
synthetic
versatility.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(16), P. 13235 - 13400
Published: Aug. 2, 2022
It
is
not
a
coincidence
that
both
chirality
and
noncovalent
interactions
are
ubiquitous
in
nature
synthetic
molecular
systems.
Noncovalent
interactivity
between
chiral
molecules
underlies
enantioselective
recognition
as
fundamental
phenomenon
regulating
life
human
activities.
Thus,
represent
the
narrative
thread
of
fascinating
story
which
goes
across
several
disciplines
medical,
chemical,
physical,
biological,
other
natural
sciences.
This
review
has
been
conceived
with
awareness
modern
attitude
toward
its
consequences
needs
to
be
founded
on
multidisciplinary
approaches
disclose
basis
essential
phenomena
domain
With
primary
aim
discussing
this
topic
an
integrated
way,
comprehensive
pool
rational
systematic
information
provided,
concerns
fundamentals
chirality,
description
interactions,
their
implications
processes
occurring
different
contexts.
A
specific
focus
devoted
enantioselection
chromatography
electromigration
techniques
because
unique
feature
"multistep"
processes.
second
motivation
for
writing
make
clear
statement
about
state
art,
tools
we
have
at
our
disposal,
what
still
missing
fully
understand
mechanisms
underlying
recognition.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(18), P. 6810 - 6816
Published: April 28, 2021
Ru(II)-catalyzed
enantioselective
C-H
functionalization
involving
an
enantiodetermining
cleavage
step
remains
undeveloped.
Here
we
describe
a
activation/annulation
of
sulfoximines
with
α-carbonyl
sulfoxonium
ylides
using
novel
class
chiral
binaphthyl
monocarboxylic
acids
as
ligands,
which
can
be
easily
and
modularly
prepared
from
1,1'-binaphthyl-2,2'-dicarboxylic
acid.
A
broad
range
sulfur-stereogenic
were
in
high
yields
excellent
enantioselectivities
(up
to
99%
yield
ee)
via
desymmetrization,
kinetic
resolution,
parallel
resolution.
Furthermore,
the
resolution
products
transformed
sulfoxides
key
intermediates
for
kinase
inhibitors.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7681 - 7724
Published: Jan. 1, 2021
Recent
advancements
in
supramolecular
catalysis
are
reviewed,
which
show
the
potential
of
related
tools
when
applied
to
organic
synthesis.
Such
recognized
as
innovative
instruments
that
can
pave
way
alternative
synthetic
strategies.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(14), P. 12308 - 12369
Published: May 20, 2022
Transition
metal
catalysis
is
of
utmost
importance
for
the
development
sustainable
processes
in
academia
and
industry.
The
activity
selectivity
complexes
are
typically
result
interplay
between
ligand
properties.
As
can
be
chemically
altered,
a
large
research
focus
has
been
on
development.
More
recently,
it
recognized
that
further
control
over
achieved
by
using
“second
coordination
sphere”,
which
seen
as
region
beyond
direct
sphere
center.
Hydrogen
bonds
appear
to
very
useful
interactions
this
context
they
have
sufficient
strength
directionality
exert
second
sphere,
yet
hydrogen
dynamic,
allowing
fast
turnover.
In
review
we
highlighted
several
key
features
bonding
summarized
use
program
sphere.
Such
bridging
two
ligands
coordinated
center
effectively
lead
supramolecular
bidentate
ligands.
addition,
used
preorganize
substrate
Both
strategies
catalysts
with
superior
properties
variety
catalyzed
transformations,
including
(asymmetric)
hydrogenation,
hydroformylation,
C–H
activation,
oxidation,
radical-type
photochemical
reactions.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(4), P. 1971 - 1985
Published: Jan. 20, 2022
Comprehensive
computational
studies
were
carried
out
to
explore
the
mechanisms
of
enantioselective
Cu/Pd
and
stereodivergent
Cu/Ir
dual-catalytic
syntheses
α,α-disubstituted
α-amino
acids
(α-AAs).
A
chiral
copper
azomethine
ylide
undergoes
facile
α-allylation
with
racemic
π-allylpalladium
species
or
stereopure
π-allyliridium
complex
stereoconvergently
stereodivergently
furnish
single/double
stereocenters,
respectively.
Stereoselectivity
at
α-center
is
controlled
by
facial
selectivity
respect
prochiral
nucleophile.
Despite
apparently
similar
transition-state
assemblies,
models
distortion/interaction
analyses
disclose
versatile
modes
stereoinduction
wherein
can
face-selectively
intercept
metal−π-allyl
intermediates
utilizing
attractive
dispersion
interactions
and/or
sterically
caused
distortions.
Generation
β-stereocenter
in
system
relies
on
a
stereospecifically
generated
allyliridium
electronically
branched-to-linear
selectivity,
while
dual
yields
linear
monochiral
product
due
steric
factors
π–π
stacking
interactions.
The
demonstrate
molecular
level
how
ligand-encoded
information
transferred
α-/β-sites
resulting
α-AAs
mode
regio-/stereoselection
altered
differences
transition-metal-stabilized
coupling
partners.
To
facilitate
stereoselective
catalysis,
suite
analytical
tools
extract
controlling
for
asymmetric
induction
demonstrated.
Science Advances,
Journal Year:
2023,
Volume and Issue:
9(16)
Published: April 21, 2023
Transition
metal–catalyzed
C─H
bond
activation
and
borylation
is
a
powerful
synthetic
method
that
offers
versatile
transformation
from
organoboron
compounds
to
virtually
all
other
functional
groups.
Compared
the
ortho-borylation,
remote
remains
more
challenging
owing
inaccessibility
of
these
bonds.
Enforcing
metal
catalyst
toward
bonds
needs
well-judged
design
through
proper
ligand
development.
This
review
article
aims
summarize
recent
discoveries
for
by
employment
new
catalyst/ligand
with
help
steric
ligand,
noncovalent
interactions.
It
has
been
found
now
takes
part
in
total
synthesis
natural
products
shorter
route.
Whereas,
Ir-catalyzed
predominant,
cobalt
also
started
affect
this
field
sustainable
cost-effective
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
ConspectusIn
contrast
to
precious
transition
metals,
such
as
palladium
and
rhodium,
the
development
of
novel
chiral
ligands
for
enantioselective
C-H
functionalizations
catalyzed
by
earth-abundant,
cost-effective,
environmentally
friendly
3d
metals
poses
substantial
challenges,
primarily
due
variable
oxidation
states,
intricate
coordination
patterns,
limited
mechanistic
insights.
In
this
Account,
we
summarize
our
research
endeavors
in
three
types
Co(III)
catalysis:
pseudotetrahedral
achiral
Cp*Co(III)/chiral
carbonyl
acid
(CCA)
catalysis,
situ-generated
octahedral
cobalt(III)
via
cobalt/salicyloxazoline
(Salox)
Co(II)/chiral
phosphoric
(CPA)
cooperative
achieved
through
strategic
ligand
design.
Our
initial
objective
was
achieve
functionalization
Cp*Co(III)
catalysts
with
external
ligands,
aiming
circumvent
laborious
preparation
CpxCo(III)
complexes.
To
end,
developed
several
CCA
incorporating
non-covalent
interactions
(NCIs)
a
crucial
design
element.
Next,
address
limitations
associated
lengthy
synthesis
Cp-ligated
complexes
difficulties
modification,
explored
concept
situ
generation
catalysis
using
commercially
available
cobalt(II)
salts
tailor-made
ligands.
This
exploration
led
two
innovative
catalytic
systems,
namely,
Co(II)/Salox
Co(II)/CCA
sequential
catalysis.
The
emerged
versatile
strategy,
demonstrating
excellent
enantioselectivities
across
range
asymmetric
reactions
construct
various
molecules
central,
axial,
planar,
inherent
chirality.
facile
single
step,
along
ease
further
enhances
versatility
applicability
approach.
Moreover,
successfully
applied
cobalt/Salox
electro-
photochemical-catalyzed
functionalization,
electrons
or
oxygen
traceless
oxidant,
thereby
eliminating
need
stoichiometric
chemical
oxidants.
Through
studies
reaction
developments,
elucidated
detailed
structure-enantioselectivity
relationships
which
are
expected
inform
future
endeavors.
Finally,
Co(II)/CPA
enabled
spiro-γ-lactams
olefination/asymmetric
[4
+
1]
spirocyclization.
Mechanistically,
establishment
stereochemistry
occurs
during
cyclization
where
CPA
serves
both
neutral
Brønsted
acid,
stereoinduction
independent
cleavage
step.
We
anticipate
that
insights
advancements
Account
will
inspire
innovations
drive
progress
metal-catalyzed
reactions.