Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 13, 2023
Trifluoroacetates
are
the
most
abundant
and
accessible
sources
of
trifluoromethyl
groups,
which
key
components
in
pharmaceuticals
agrochemicals.
The
generation
reactive
radicals
from
trifluoroacetates
requires
their
decarboxylation,
is
hampered
by
high
oxidation
potential.
This
constitutes
a
major
challenge
for
redox-based
methods,
because
need
to
pair
redox
potentials
with
trifluoroacetate.
Here
we
report
strategy
based
on
iron
photocatalysis
promote
direct
photodecarboxylation
that
displays
reactivity
features
escape
limitations.
Our
synthetic
design
has
enabled
use
trifluoromethylation
more
easily
oxidizable
organic
substrates,
offering
new
opportunities
late-stage
derivatization
campaigns
using
chemical
feedstocks,
Earth-abundant
catalysts,
visible-light.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1875 - 1924
Published: Aug. 6, 2021
Direct
photocatalyzed
hydrogen
atom
transfer
(d-HAT)
can
be
considered
a
method
of
choice
for
the
elaboration
aliphatic
C–H
bonds.
In
this
manifold,
photocatalyst
(PCHAT)
exploits
energy
photon
to
trigger
homolytic
cleavage
such
bonds
in
organic
compounds.
Selective
bond
may
achieved
by
judicious
abstractor
(key
parameters
are
electronic
character
and
molecular
structure),
as
well
reaction
additives.
Different
classes
PCsHAT
available,
including
aromatic
ketones,
xanthene
dyes
(Eosin
Y),
polyoxometalates,
uranyl
salts,
metal-oxo
porphyrin
tris(amino)cyclopropenium
radical
dication.
The
processes
(mainly
C–C
formation)
most
cases
carried
out
under
mild
conditions
with
help
visible
light.
aim
review
is
offer
comprehensive
survey
synthetic
applications
d-HAT.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2292 - 2352
Published: Dec. 9, 2021
The
halogen-atom
transfer
(XAT)
is
one
of
the
most
important
and
applied
processes
for
generation
carbon
radicals
in
synthetic
chemistry.
In
this
review,
we
summarize
highlight
aspects
associated
with
XAT
impact
it
has
had
on
photochemistry
photocatalysis.
organization
material
starts
analysis
mechanistic
then
follows
a
subdivision
based
nature
reagents
used
halogen
abstraction.
This
review
aims
to
provide
general
overview
fundamental
concepts
main
agents
involved
objective
offering
tool
understand
facilitate
development
new
radical
strategies.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1626 - 1653
Published: July 6, 2021
For
molecules
with
a
singlet
ground
state,
the
population
of
triplet
states
is
mainly
possible
(a)
by
direct
excitation
and
subsequent
intersystem
crossing
or
(b)
energy
transfer
from
an
appropriate
sensitizer.
The
latter
scenario
enables
catalytic
photochemical
reaction
in
which
sensitizer
adopts
role
catalyst
undergoing
several
cycles
photon
absorption
to
substrate.
If
product
molecule
triplet-sensitized
process
chiral,
this
can
proceed
enantioselectively
upon
judicious
choice
chiral
An
enantioselective
also
occur
dual
approach
which,
apart
achiral
sensitizer,
second
activates
substrate
toward
sensitization.
Although
idea
reactions
via
intermediates
has
been
pursued
for
more
than
50
years,
notable
selectivities
exceeding
90%
enantiomeric
excess
(ee)
have
only
realized
past
decade.
This
review
attempts
provide
comprehensive
survey
on
various
were
rendered
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1717 - 1751
Published: July 7, 2021
Recent
progress
in
the
development
of
photocatalytic
reactions
promoted
by
visible
light
is
leading
to
a
renaissance
use
photochemistry
construction
structurally
elaborate
organic
molecules.
Because
rich
functionality
found
natural
products,
studies
product
total
synthesis
provide
useful
insights
into
functional
group
compatibility
these
new
methods
as
well
their
impact
on
synthetic
strategy.
In
this
review,
we
examine
syntheses
published
through
end
2020
that
employ
visible-light
photoredox
catalytic
step.
To
assist
someone
interested
employing
steps
discussed,
review
organized
largely
nature
bond
formed
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(3), P. 1640 - 1683
Published: Jan. 20, 2021
The
past
decade
has
witnessed
the
emergence
of
N-(acyloxy)phthalimides
(NHPI
esters)
and
its
derivatives
at
forefront
synthetic
methods
facilitating
construction
diverse
molecular
frameworks
from
readily
available
carboxylic
acid
feedstock.
NHPI
esters
are
predisposed
to
undergo
reductive
fragmentation
via
a
single
electron
transfer
(SET)
process
under
thermal,
photochemical,
or
electrochemical
conditions
generate
corresponding
carbon-
nitrogen-centered
radicals
that
participate
in
multitude
transformations
forge
carbon–carbon
carbon–heteroatom
bonds.
chemistry
involving
received
broad
applicability
not
only
well-designed
cascade
annulations
but
also
medicinal
natural
product
synthesis.
This
comprehensive
Review,
broadly
categorized
according
nature
bond
formation,
details
progress
made
this
field
since
initial
discovery
by
providing
representative
examples
with
mechanistic
details,
an
emphasis
on
challenges
future
directions.
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.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(20), P. 12784 - 12965
Published: Aug. 27, 2021
This
review
serves
to
document
advances
in
the
synthesis,
versatile
bonding,
and
reactivity
of
molecular
main
group
metal
hydrides
within
Groups
1,
2,
12–16.
Particular
attention
will
be
given
emerging
use
said
rapidly
expanding
field
Main
Group
element-mediated
catalysis.
While
this
is
comprehensive
nature,
focus
research
appearing
open
literature
since
2001.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(28), P. 12567 - 12583
Published: July 11, 2022
Visible-light
photocatalysis
and
electrocatalysis
are
two
powerful
strategies
for
the
promotion
of
chemical
reactions
that
have
received
tremendous
attention
in
recent
years.
In
contrast,
processes
combine
these
modalities,
an
area
termed
electrophotocatalysis,
until
recently
remained
quite
rare.
However,
over
past
several
years
a
number
reports
this
shown
potential
combining
power
light
electrical
energy
to
realize
new
catalytic
transformations.
Electrophotocatalysis
offers
ability
perform
photoredox
without
need
large
quantities
stoichiometric
or
superstoichiometric
oxidants
reductants
by
making
use
electrochemical
as
electron
source
sink.
addition,
electrophotocatalysis
is
readily
amenable
generation
open-shell
photocatalysts,
which
tend
exceptionally
strong
redox
potentials.
way,
potent
yet
selective
been
realized
under
relatively
mild
conditions.
This
Perspective
highlights
advances
provides
some
possible
avenues
future
work
growing
area.
