Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(10), P. 4121 - 4130
Published: Jan. 8, 2020
Abstract
The
construction
of
diverse
sp
3
‐rich
skeletal
ring
systems
is
importance
to
drug
discovery
programmes
and
natural
product
synthesis.
Herein,
we
report
the
photocatalytic
2,7‐diazabicyclo[3.2.1]octanes
(bridged
1,3‐diazepanes)
via
a
reductive
diversion
Minisci
reaction.
fused
tricyclic
proposed
form
radical
addition
C4
position
4‐substituted
quinoline
substrates,
with
subsequent
Hantzsch
ester‐promoted
reduction
dihydropyridine
intermediate
which
undergoes
in
situ
two‐electron
closure
bridged
diazepane
architecture.
A
wide
scope
N‐arylimine
derivatives
was
demonstrated
good
efficiency
observed
sterically
congested
all‐carbon
quaternary
centers.
Computational
experimental
mechanistic
studies
provided
insights
into
reaction
mechanism
regioselectivity/diastereoselectivity.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2017 - 2291
Published: Nov. 23, 2021
We
present
here
a
review
of
the
photochemical
and
electrochemical
applications
multi-site
proton-coupled
electron
transfer
(MS-PCET)
in
organic
synthesis.
MS-PCETs
are
redox
mechanisms
which
both
an
proton
exchanged
together,
often
concerted
elementary
step.
As
such,
MS-PCET
can
function
as
non-classical
mechanism
for
homolytic
bond
activation,
providing
opportunities
to
generate
synthetically
useful
free
radical
intermediates
directly
from
wide
variety
common
functional
groups.
introduction
practitioner’s
guide
reaction
design,
with
emphasis
on
unique
energetic
selectivity
features
that
characteristic
this
class.
then
chapters
oxidative
N–H,
O–H,
S–H,
C–H
homolysis
methods,
generation
corresponding
neutral
species.
Then,
reductive
PCET
activations
involving
carbonyl,
imine,
other
X═Y
π-systems,
heteroarenes,
where
ketyl,
α-amino,
heteroarene-derived
radicals
be
generated.
Finally,
we
asymmetric
catalysis
materials
device
applications.
Within
each
chapter,
subdivide
by
group
undergoing
homolysis,
thereafter
type
transformation
being
promoted.
Methods
published
prior
end
December
2020
presented.
Organic & Biomolecular Chemistry,
Journal Year:
2019,
Volume and Issue:
17(29), P. 6936 - 6951
Published: Jan. 1, 2019
This
minireview
highlights
the
recent
advances
in
chemistry
of
Hantzsch
esters
photoredox
catalyzed
organic
synthesis,
with
particular
emphasis
placed
on
reaction
mechanisms.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(6), P. 5842 - 5976
Published: Jan. 24, 2022
Benefiting
from
the
impressive
increase
in
fundamental
knowledge,
last
20
years
have
shown
a
continuous
burst
of
new
ideas
and
consequently
plethora
catalytic
methods
for
enantioselective
radical
reactions.
This
review
aims
to
provide
complete
survey
progress
achieved
over
this
latter
period.
The
first
part
focuses
on
use
chiral
organocatalysts,
these
include
catalysts
covalently
linked
substrate
those
that
interact
with
by
weaker
interactions
like
hydrogen
bonds.
second
is
devoted
transition-metal
redox
catalysis
which
organized
according
increasing
atomic
number
first-row
transition
metals
(Ti,
Cr,
Fe,
Mn,
Co,
Ni,
Cu).
Bioinspired
manganese-
iron-mediated
hydroxylations
oxidations
are
also
discussed.
A
specific
section
dedicated
reactivity
Ru,
Rh,
Ir
complexes
as
Lewis
acids
special
focus
at
metal.
Absorption
photons
result
different
events
such
energy
transfer,
single-electron
hydrogen-atom
transfer
facilitating
formation
radicals.
Organocatalysis
has
been
successfully
combined
photocatalysts,
opened
pathways
enlarging
precursors
available.
merger
photocatalysis
organo-
or
metalla-photocatalysis
brought
novelty
allowed
discovery
large
original
transformations.
enzyme-catalyzed
reactions
involving
intermediates
largely
benefit
visible-light
irradiation
included
review.
provides
comprehensive
inventory
goal
detailing
reaction
mechanisms
involved
transformations
any
nonspecialist
could
find
their
own
creativity
invent
yet
unknown
applications.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(7), P. 3636 - 3644
Published: Jan. 31, 2020
In
the
past
decades,
significant
advances
have
been
made
on
radical
Smiles
rearrangement.
However,
eventually
formed
intermediates
in
these
reactions
are
limited
to
amidyl
radical,
except
for
few
examples
initiated
by
a
N-centered
radical.
Here,
novel
and
practical
rearrangement
triggered
photoredox-catalyzed
regioselective
ketyl-ynamide
coupling
is
reported,
which
represents
first
of
ynamides.
This
method
enables
facile
access
variety
valuable
2-benzhydrylindoles
with
broad
substrate
scope
generally
good
yields
under
mild
reaction
conditions.
addition,
this
chemistry
can
also
be
extended
divergent
synthesis
versatile
3-benzhydrylisoquinolines
through
similar
rearrangement,
followed
dehydrogenative
oxidation.
Moreover,
such
an
ynamide
intermolecular
photoredox
catalysis
via
addition
external
sources
achieved.
By
control
experiments,
was
shown
proceed
key
ketyl
α-imino
carbon
intermediates.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(3), P. 2009 - 2025
Published: Jan. 21, 2020
The
construction
and
manipulation
of
amine-containing
architectures
is
importance
to
academic
industrial
development
discovery
programs.
photochemical
single-electron
reduction
imine
derivatives
generate
α-amino
radical
intermediates
has
emerged
as
a
powerful
umpolung
strategy
for
opening
up
underexplored
routes
such
amine
motifs.
Furthermore,
these
radicals
have
been
shown
engage
in
wide
variety
chemistry,
including
radical–radical
coupling,
addition
electrophiles,
reductive
amination
chemistry.
concept
also
begun
see
application
iminium
ion
the
extension
enantiocontrolled
C–C
bond
formation.
This
Perspective
covers
recent
efforts
this
synthetic
simple
complex
structures
alike.
Synlett,
Journal Year:
2021,
Volume and Issue:
33(12), P. 1154 - 1179
Published: Feb. 15, 2021
Abstract
Photoredox
catalysis
has
proven
to
be
a
powerful
tool
in
synthetic
organic
chemistry.
The
rational
design
of
photosensitizers
with
improved
photocatalytic
performance
constitutes
major
advancement
photoredox
transformations.
This
review
summarizes
the
fundamental
ground-state
and
excited-state
photophysical
electrochemical
attributes
molecular
photosensitizers,
which
are
important
determinants
their
reactivity.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 8372 - 8380
Published: March 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.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 18, 2025
Chiral
phosphoric
acids
(CPAs)
have
emerged
as
highly
effective
Brønsted
acid
catalysts
in
an
expanding
range
of
asymmetric
transformations,
often
through
novel
multifunctional
substrate
activation
modes.
Versatile
and
broadly
appealing,
these
benefit
from
modular
tunable
structures,
compatibility
with
additives.
Given
the
unique
types
noncovalent
interactions
(NCIs)
that
can
be
established
between
CPAs
various
reactants─such
hydrogen
bonding,
aromatic
interactions,
van
der
Waals
forces─it
is
unsurprising
catalyst
systems
become
a
promising
approach
for
accessing
diverse
chiral
product
outcomes.
This
review
aims
to
provide
in-depth
exploration
mechanisms
by
which
impart
stereoselectivity,
positioning
NCIs
central
feature
connects
broad
spectrum
catalytic
reactions.
Spanning
literature
2004
2024,
it
covers
nucleophilic
additions,
radical
atroposelective
bond
formations,
highlighting
applicability
CPA
organocatalysis.
Special
emphasis
placed
on
structural
mechanistic
features
govern
CPA-substrate
well
tools
techniques
developed
enhance
our
understanding
their
behavior.
In
addition
emphasizing
details
stereocontrolling
elements
individual
reactions,
we
carefully
structured
this
natural
progression
specifics
broader,
class-level
perspective.
Overall,
findings
underscore
critical
role
catalysis
significant
contributions
advancing
synthesis.
Chemical Science,
Journal Year:
2019,
Volume and Issue:
11(6), P. 1494 - 1502
Published: Dec. 19, 2019
Covalent
organic
frameworks
(COFs)
show
great
promise
as
heterogeneous
photocatalysts,
but
they
have
not
yet
been
explored
for
asymmetric
photocatalysis,
which
is
important
the
sustainable
production
of
pharmaceuticals
and
fine
chemicals.