Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(40), С. 18195 - 18211
Опубликована: Сен. 30, 2022
Electrostatic
attraction
between
two
groups
of
opposite
charge,
typically
known
as
ion-pairing,
offers
unique
opportunities
for
the
design
systems
to
enable
selectivity
control
in
chemical
reactions.
Catalysis
using
noncovalent
interactions
is
an
established
and
vibrant
research
area,
but
it
noticeable
that
hydrogen
bonding
are
still
main
interaction
choice
system
design.
Opposite
charges
experience
powerful
force
Coulombic
have
ability
exert
fundamental
influence
on
outcome
reactions
involve
charged
reagents,
intermediates
or
catalysts.
In
this
Perspective,
we
will
examine
how
ion-pairing
been
used
C-H
bond
functionalization
processes.
This
broad
class
provides
interesting
thought-provoking
lens
through
which
application
strategies
because
one
encompasses
great
mechanistic
diversity,
poses
significant
challenges,
perhaps
most
importantly
immense
interest
synthetic
chemists
both
industry
academia.
We
survey
proceed
via
radical
ionic
mechanisms
alongside
those
transition
metal
catalysis
deal
with
site-selectivity
enantioselectivity.
anticipate
emerging
area
develops,
become
ever-more
important
strategy
control.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(38), С. 17319 - 17329
Опубликована: Сен. 1, 2022
The
enantioconvergent
cross-coupling
of
racemic
alkyl
halides
represents
a
powerful
tool
for
the
synthesis
enantioenriched
molecules.
In
this
regard,
first-row
transition
metal
catalysis
provides
suitable
mechanism
stereoconvergence
by
converting
to
prochiral
radical
intermediates
owing
their
good
single-electron
transfer
ability.
contrast
noble
development
chiral
nickel
catalyst,
copper-catalyzed
is
less
studied.
Besides
enantiocontrol
issue,
major
challenge
arises
from
weak
reducing
capability
copper
that
slows
reaction
initiation.
Recently,
significant
efforts
have
been
dedicated
basic
research
aimed
at
developing
ligands
halides.
This
perspective
will
discuss
advances
in
burgeoning
area
with
particular
emphasis
on
strategic
anionic
ligand
design
tune
initiation
under
thermal
conditions
our
group.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(13), С. 6040 - 6049
Опубликована: Март 24, 2022
Axially
chiral
biaryls
and
heterobiaryls
constitute
the
most
represented
subclass
of
atropisomers
with
prevalence
in
natural
products,
bioactive
compounds,
privileged
ligand/catalysts,
optically
pure
materials.
Despite
many
ionic
protocols
for
their
construction,
radical-based
variants
represent
another
highly
desirable
intriguing
strategy
but
are
far
less
developed.
Moreover,
efficient
synthesis
axially
heterobiaryl
molecules,
especially
ones
having
multiple
heteroatoms
other
types
elements,
through
radical
routes
remains
extremely
limited.
We
herein
disclose
first
catalytic
asymmetric,
metal-free
construction
centrally
by
Minisci
reaction
5-arylpyrimidines
α-amino
acid-derived
redox-active
esters.
This
is
enabled
use
4CzIPN
as
an
organic
photoredox
catalyst
conjunction
a
phosphoric
acid
catalyst.
The
achieved
variety
interesting
featuring
union
α-branched
amine
generally
excellent
regio-,
diastereo-,
enantioselectivity
(up
to
82%
yield;
>19:1
dr;
>99%
ee).
finding
also
builds
up
new
platform
development
desymmetrization
methods
via
radical-involved
atroposelective
functionalization
at
heteroarene
prochiral
heterobiaryls.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(12), С. 8372 - 8380
Опубликована: Март 18, 2024
Here
we
present
a
highly
enantioselective
[2π
+
2σ]
photocycloaddition
of
bicyclo[1.1.0]butanes
(BCBs).
The
reaction
uses
variety
vinylazaarenes
as
partners
and
is
catalyzed
by
polycyclic
aromatic
hydrocarbon
(PAH)-containing
chiral
phosphoric
acid
bifunctional
photosensitizer.
A
wide
array
pharmaceutically
important
bicyclo[2.1.1]hexane
(BCH)
derivatives
have
been
synthesized
with
high
yields,
enantioselectivity,
diastereoselectivity.
In
addition
to
the
diverse
1-ketocarbonyl-3-substituted
BCBs,
α/β-substituted
are
compatible
such
an
unprecedented
photoredox
catalytic
pathway,
resulting
in
successful
assembly
all-carbon
quaternary
stereocenter
or
two
adjacent
tertiary
stereocenters
on
product.
Advanced Materials,
Год журнала:
2023,
Номер
35(16)
Опубликована: Янв. 6, 2023
Macrocycles
with
well-defined
cavities
and
the
ability
to
undergo
supramolecular
interactions
are
classical
materials
that
have
played
an
essential
role
in
science.
However,
one
of
most
substantial
barriers
limiting
utilization
macrocycles
is
their
aggregation,
which
blocks
active
regions.
Among
many
attempted
strategies
prevent
such
installing
into
covalent
organic
frameworks
(COFs),
porous
stable
reticular
networks,
has
emerged
as
ideal
solution.
The
resulting
macrocycle-based
COFs
(M-COFs)
preserve
macrocycles'
unique
activities,
enabling
applications
various
fields
single-atom
catalysis,
adsorption/separation,
optoelectronics,
phototherapy,
structural
design
forming
single-layered
or
mechanically
interlocked
COFs.
properties
unmatchable
by
any
combination
other
substrates,
opening
a
new
chapter
advanced
materials.
This
review
focuses
on
latest
progress
concepts,
synthesis,
properties,
M-COFs,
presents
in-depth
outlook
challenges
opportunities
this
emerging
field.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(9), С. 5231 - 5241
Опубликована: Фев. 22, 2023
The
selective
functionalization
of
ubiquitous
but
inert
C-H
bonds
is
highly
appealing
in
synthetic
chemistry,
the
direct
transformation
hydrocarbons
lacking
directing
groups
into
high-value
chiral
molecules
remains
a
formidable
challenge.
Herein,
we
develop
an
enantioselective
C(sp3)-H
undirected
oxacycles
via
photo-HAT/nickel
dual
catalysis.
This
protocol
provides
practical
platform
for
rapid
construction
and
enantiomerically
enriched
directly
from
simple
abundant
hydrocarbon
feedstocks.
utility
this
strategy
further
demonstrated
late-stage
natural
products
synthesis
many
pharmaceutically
relevant
molecules.
Experimental
density
functional
theory
calculation
studies
provide
detailed
insights
mechanism
origin
enantioselectivity
asymmetric
functionalization.
