Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(50), P. 17433 - 17438
Published: Dec. 5, 2018
A
strategy
for
the
installation
of
small
alkyl
fragments
onto
pharmaceutically
relevant
aliphatic
structures
has
been
established
via
metallaphotoredox
catalysis.
Herein,
we
report
that
tris(trimethylsilyl)silanol
can
be
employed
as
an
effective
halogen
abstraction
reagent
that,
in
combination
with
photoredox
and
nickel
catalysis,
allows
a
generic
approach
to
Csp3–Csp3
cross-electrophile
coupling.
In
this
study,
demonstrate
variety
drug-like
groups
successfully
coupled
number
commercially
available
electrophiles,
including
methyl
tosylate
strained
cyclic
bromides.
Moreover,
union
two
secondary
carbon
centers,
long-standing
challenge
organic
molecule
construction,
accomplished
wide
array
structural
formats.
Last,
technology
selectively
merged
Csp2–Csp3
aryl–alkyl
couplings
build
systems
highly
modular
fashion.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(16), P. 9170 - 9196
Published: July 20, 2020
The
development
of
transition
metal
(TM)
catalysis
for
organic
synthesis
under
visible
light
without
recourse
to
typical
photoredox
catalysts
has
become
a
rapidly
growing
area
research
and
been
actively
explored
in
the
past
several
years.
Distinct
from
extensively
developed
catalysis,
which
photocatalyst
generally
does
not
directly
participate
bond-forming
process,
photocatalyst/TM
synergistic
absorbs
photon
energy
transfers
TM
catalyst
through
redox
or
transfer
this
Review
focuses
on
summarizing
recent
developments
photocatalytic
reactions
that
use
complexes
both
absorb
catalytic
bond
formation
involving
covalently
bonded
intermediate.
contents
are
categorized
by
used
(Pd,
Cu,
Co,
Ni,
Mn,
Au,
Rh,
Fe,
Ru),
with
descending
sequence
according
number
examples
reported
each
metal,
provide
an
overview
April
2020.
Future
perspectives
personal
opinions
regarding
expanding
field
also
discussed.
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 Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(11), P. 6308 - 6319
Published: Jan. 1, 2021
Radical
trifluoromethylation
has
been
emerging
as
a
versatile
tool
for
the
synthesis
of
trifluoromethylated
compounds
that
play
increasingly
important
roles
in
pharmaceuticals,
agrochemicals
and
materials
science.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(3), P. 1670 - 1715
Published: Dec. 31, 2020
Fluorinated
pyrazoles
play
an
important
role
in
medicinal
chemistry,
drug
discovery,
agrochemistry,
coordination
and
organometallic
chemistry.
Since
the
early
1990s,
their
popularity
has
grown
exponentially.
Moreover,
more
than
50%
of
all
contributions
on
topic
have
been
published
last
5
years.
In
this
review,
analysis
novel
synthetic
approaches
to
fluorinated
that
appeared
recent
years
is
performed.
A
particular
emphasis
devoted
a
detailed
consideration
reaction
mechanisms.
addition,
reasons
led
ever-increasing
various
areas
science
are
discussed.
At
end
several
potentially
interesting
but
yet
mostly
unknown
classes
outlined.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(33), P. 13203 - 13211
Published: Aug. 1, 2019
Fluorinated
organic
molecules
are
pervasive
within
the
pharmaceutical
and
agrochemical
industries
due
to
range
of
structural
physicochemical
properties
that
fluorine
imparts.
Currently,
most
abundant
methods
for
synthesis
aryl–CF2
functionality
have
relied
on
deoxyfluorination
ketones
aldehydes
using
expensive
poorly
atom
economical
reagents.
Here,
we
report
a
general
method
aryl–CF2R
aryl–CF2H
compounds
through
activation
corresponding
trifluoromethyl
arene
precursors.
This
strategy
is
enabled
by
an
endergonic
electron
transfer
event
provides
access
radical
anions
lie
outside
catalyst
reduction
potential.
Fragmentation
these
reactive
intermediates
delivers
difluorobenzylic
radicals
can
be
intercepted
alkene
feedstocks
or
hydrogen
provide
diverse
array
difluoalkylaromatics.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(37), P. 15830 - 15841
Published: Aug. 4, 2020
The
combined
use
of
reaction
kinetic
analysis,
ultrafast
spectroscopy,
and
stoichiometric
organometallic
studies
has
enabled
the
elucidation
mechanistic
underpinnings
to
a
photocatalytic
C-N
cross-coupling
reaction.
Steady-state
spectroscopic
techniques
were
used
track
excited-state
evolution
employed
iridium
photocatalyst,
determine
resting
states
both
nickel
catalysts,
uncover
photochemical
mechanism
for
reductive
activation
cocatalyst.
Stoichiometric
along
with
comprehensive
study
reaction,
including
rate-driving
force
unveiled
crucial
role
photocatalysis
in
initiating
sustaining
Ni(I)/Ni(III)
mechanism.
insights
gleaned
from
this
further
discovery
new
photocatalyst
providing
>30-fold
rate
increase.
