Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(14), P. 6185 - 6192
Published: March 30, 2022
Alcohols
and
carboxylic
acids
are
among
the
most
commercially
abundant,
synthetically
versatile,
operationally
convenient
functional
groups
in
organic
chemistry.
Under
visible
light
photoredox
catalysis,
these
native
synthetic
handles
readily
undergo
radical
activation,
resulting
open-shell
intermediates
can
subsequently
participate
transition
metal
catalysis.
In
this
report,
we
describe
C(sp3)–C(sp3)
cross-coupling
of
alcohols
through
dual
combination
N-heterocyclic
carbene
(NHC)-mediated
deoxygenation
hypervalent
iodine-mediated
decarboxylation.
This
mild
practical
Ni-catalyzed
radical-coupling
protocol
was
employed
to
prepare
a
wide
array
alkyl–alkyl
cross-coupled
products,
including
highly
congested
quaternary
carbon
centers
from
corresponding
tertiary
or
acids.
We
demonstrate
applications
methodology
alcohol
C1-alkylation
formal
homologation,
as
well
late-stage
functionalization
drugs,
natural
biomolecules.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2487 - 2649
Published: Nov. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
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.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2907 - 2980
Published: Sept. 24, 2021
In
the
pursuit
of
new
pharmaceuticals
and
agrochemicals,
chemists
in
life
science
industry
require
access
to
mild
robust
synthetic
methodologies
systematically
modify
chemical
structures,
explore
novel
space,
enable
efficient
synthesis.
this
context,
photocatalysis
has
emerged
as
a
powerful
technology
for
synthesis
complex
often
highly
functionalized
molecules.
This
Review
aims
summarize
published
contributions
field
from
industry,
including
research
industrial-academic
partnerships.
An
overview
developed
strategic
applications
synthesis,
peptide
functionalization,
isotope
labeling,
both
DNA-encoded
traditional
library
is
provided,
along
with
summary
state-of-the-art
photoreactor
effective
upscaling
photocatalytic
reactions.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(14), P. 8868 - 8925
Published: Jan. 25, 2021
Within
the
wide
family
of
gold-catalyzed
reactions,
gold
photocatalysis
intrinsically
features
unique
elementary
steps.
When
catalysis
meets
photocatalysis,
a
valence
change
center
can
easily
be
achieved
via
electron
transfer
and
radical
addition,
avoiding
use
stoichiometric
sacrificial
external
oxidants.
The
excellent
compatibility
radicals
with
catalysts
opens
door
to
series
important
organic
transformations,
including
redox-neutral
C–C
C–X
coupling,
C–H
activation,
formal
radical–radical
cross-coupling.
complexes
nicely
complements
existing
photoredox
strategies
also
new
avenue
for
chemistry.
This
review
covers
transformations
both
mononuclear
gold(I)
(with
without
photosensitizer)
dinuclear
photocatalysts.
Various
fascinating
methodologies,
their
value
chemists,
current
mechanistic
understanding
are
discussed.
most
recent
examples
demonstrate
feasibility
both,
participate
in
excited
state
energy
(EnT),
rather
than
transfer.
rare
applications
gold(III)
photocatalysts,
homogeneous
heterogeneous,
summarized.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(12), P. 6862 - 6869
Published: June 8, 2020
N-Heterocyclic
carbene
(NHC)
organocatalysis
to
promote
so-called
umpolung
reactions
has
emerged
as
a
powerful
tool
for
modern
organic
synthesis.
NHC-bound
nucleophiles
known
Breslow
intermediates
can
be
obtained
by
reacting
an
NHC
catalyst
with
aldehyde
and
will
add
carbon–heteroatom
or
carbon–carbon
double
bonds.
On
the
other
hand,
substitution-type
cross-couplings
of
carbon
electrophiles
(that
is,
R–X
species)
generate
bonds
have
also
been
demonstrated
even
though
such
processes
are
difficult
less
mature
at
present.
This
Perspective
briefly
summarizes
NHC-based
catalysis
enabling
cross-coupling
reactions.
Three
types
systems
examined:
anionic,
hybrid,
radical
catalysis.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2353 - 2428
Published: Oct. 8, 2021
For
more
than
70
years,
nitrogen-centered
radicals
have
been
recognized
as
potent
synthetic
intermediates.
This
review
is
a
survey
designed
for
use
by
chemists
engaged
in
target-oriented
synthesis.
summarizes
the
recent
paradigm
shift
access
to
and
application
of
N-centered
enabled
visible-light
photocatalysis.
broadens
streamlines
approaches
many
small
molecules
because
photocatalysis
conditions
are
mild.
Explicit
attention
paid
innovative
advances
N–X
bonds
radical
precursors,
where
X
=
Cl,
N,
S,
O,
H.
clarity,
key
mechanistic
data
noted,
available.
Synthetic
applications
limitations
summarized
illuminate
tremendous
utility
photocatalytically
generated
radicals.
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.