Science Advances,
Journal Year:
2024,
Volume and Issue:
10(14)
Published: April 5, 2024
Direct
conversion
of
hydrocarbons
into
amines
represents
an
important
and
atom-economic
goal
in
chemistry
for
decades.
However,
intermolecular
cross-coupling
terminal
alkenes
with
to
form
branched
remains
extremely
challenging.
Here,
a
visible-light
Co-dual
catalyzed
direct
allylic
C─H
amination
free
afford
has
been
developed.
Notably,
challenging
aliphatic
strong
coordinating
effect
can
be
directly
used
as
C─N
coupling
partner
couple
bond
advanced
molecular
complexity.
Moreover,
the
reaction
proceeds
exclusive
regio-
chemoselectivity
at
more
steric
hinder
position
deliver
primary,
secondary,
tertiary
diverse
substitution
patterns
that
are
difficult
access
otherwise.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(9)
Published: Nov. 14, 2023
Visible
light-induced
Pd
catalysis
has
emerged
as
a
promising
subfield
of
photocatalysis.
The
hybrid
nature
radical
species
enabled
wide
array
radical-based
transformations
otherwise
challenging
or
unknown
via
conventional
chemistry.
In
parallel
to
the
ongoing
pursuit
alternative,
readily
available
precursors,
notable
discoveries
have
demonstrated
that
photoexcitation
can
alter
not
only
oxidative
addition
but
also
other
elementary
steps.
This
Minireview
highlights
recent
progress
in
this
area.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1209 - 1223
Published: Jan. 3, 2024
Owing
to
its
diverse
activation
processes
including
single-electron
transfer
(SET)
and
hydrogen-atom
(HAT),
visible-light
photocatalysis
has
emerged
as
a
sustainable
efficient
platform
for
organic
synthesis.
These
provide
powerful
avenue
the
direct
functionalization
of
C(sp3)–H
bonds
under
mild
conditions.
Over
past
decade,
there
have
been
remarkable
advances
in
enantioselective
bond
via
combined
with
conventional
asymmetric
catalysis.
Herein,
we
summarize
involving
discuss
two
main
pathways
this
emerging
field:
(a)
SET-driven
carbocation
intermediates
are
followed
by
stereospecific
nucleophile
attacks;
(b)
photodriven
alkyl
radical
further
enantioselectively
captured
(i)
chiral
π-SOMOphile
reagents,
(ii)
stereoselective
transition-metal
complexes,
(iii)
another
distinct
stereoscopic
species.
We
aim
key
reaction
design,
catalyst
development,
mechanistic
understanding,
new
insights
into
rapidly
evolving
area
research.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(17), P. 12053 - 12062
Published: April 16, 2024
Three-component
diene
carboaminations
offer
a
potent
means
to
access
synthetically
valuable
allylic
amines
with
rapid
molecular
complexity
escalation.
The
existing
literature
primarily
discloses
racemic
examples,
necessitating
the
use
of
halides/pseudohalides
as
substrates.
This
paper
introduces
photoinduced
Pd-catalyzed
enantioselective
three-component
carboamination
aryl-substituted
1,3-dienes,
leveraging
aliphatic
C–H
bonds
for
synthesis.
reaction
employs
10
mol
%
chiral
palladium
catalyst
and
an
excess
aryl
bromide
HAT
reagent.
approach
yields
diverse
allylamines
moderate
excellent
enantioselectivities.
Notably,
it
stands
first
instance
asymmetric
reaction,
directly
utilizing
abundant
C(sp3)–H
bearing
partners,
such
toluene-type
substrates,
ethers,
amines,
esters,
ketones.
protocol
exhibits
versatility
across
encompassing
aliphatic,
aromatic,
primary,
secondary
derivatives.
method
could
serve
versatile
platform
stereoselective
incorporation
various
nucleophiles,
dienes,
partners.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(14)
Published: Feb. 9, 2024
Abstract
A
visible‐light‐induced,
three‐component
palladium‐catalyzed
1,4‐aminoarylation
of
butadienes
with
readily
available
aryl
halides
and
aliphatic
amines
has
been
developed,
affording
allylamines
excellent
E
‐selectivity.
The
reaction
exhibits
exceptional
control
over
chemo‐,
regio‐,
stereoselectivity,
a
broad
substrate
scope,
high
functional
group
compatibility,
as
demonstrated
by
the
late‐stage
functionalization
bioactive
molecules.
Mechanistic
investigations
are
consistent
photoinduced
radical
Pd(0)‐Pd(I)‐Pd(II)‐Pd(0)
Heck‐Tsuji–Trost
allylation
cascade.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 4665 - 4680
Published: March 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(22), P. 12224 - 12232
Published: May 24, 2023
Photoinduced
enhancement
of
hydricity
palladium
hydride
species
enables
unprecedented
addition-like
(“hydridic”)
hydropalladation
electron-deficient
alkenes,
which
allows
for
chemoselective
head-to-tail
cross-hydroalkenylation
and
electron-rich
alkenes.
This
mild
general
protocol
works
with
a
wide
range
densely
functionalized
complex
Notably,
this
approach
also
highly
challenging
cross-dimerization
electronically
diverse
vinyl
arenes
heteroarenes.
Molecules,
Journal Year:
2023,
Volume and Issue:
28(16), P. 6127 - 6127
Published: Aug. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts