Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(7), P. 3532 - 3539
Published: Feb. 4, 2020
Cross-coupling
reactions
for
carbon–carbon
and
carbon–heteroatom
bond
formation
are
of
great
importance
in
modern
chemical
synthesis.
In
addition
to
classical
cross-couplings
involving
preformed
or
preactivated
coupling
partners,
more
recently
breakthroughs
have
been
made
the
selective,
direct
abundant
aliphatic
carbon–hydrogen
bonds
using
hydrogen
atom
transfer
which
bond-dissociation
energy
is
thermodynamic
driving
force.
The
challenging
activation
still
rather
underdeveloped
due
inertness.
Herein,
we
report
a
mild
general
strategy
diverse
set
readily
available
cyclic
alcohols
remote
site-specific
arylation
ketones
via
combination
photoredox-mediated
multisite
concerted
proton–electron
(MS-PCET)
nickel
catalysis.
current
cross-coupling
proceeds
with
generation
an
alkoxy
radical
utilizing
free
(BDFE)
as
Subsequently,
resulting
carbon-centered
radicals
formed
by
C–C
cleavage
merge
catalytic
cycle
create
C(sp3)–C(sp2)
bonds.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1485 - 1542
Published: Nov. 18, 2021
The
merger
of
photoredox
catalysis
with
transition
metal
catalysis,
termed
metallaphotoredox
has
become
a
mainstay
in
synthetic
methodology
over
the
past
decade.
Metallaphotoredox
combined
unparalleled
capacity
for
bond
formation
broad
utility
photoinduced
electron-
and
energy-transfer
processes.
Photocatalytic
substrate
activation
allowed
engagement
simple
starting
materials
metal-mediated
bond-forming
Moreover,
electron
or
energy
transfer
directly
key
organometallic
intermediates
provided
novel
modes
entirely
complementary
to
traditional
catalytic
platforms.
This
Review
details
contextualizes
advancements
molecule
construction
brought
forth
by
metallaphotocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(1), P. 74 - 108
Published: May 22, 2019
Abstract
Radical–radical
couplings
are
mostly
nearly
diffusion‐controlled
processes.
Therefore,
the
selective
cross‐coupling
of
two
different
radicals
is
challenging
and
not
a
synthetically
valuable
transformation.
However,
if
have
lifetimes
they
generated
at
equal
rates,
will
become
dominant
process.
This
high
cross‐selectivity
based
on
kinetic
phenomenon
called
persistent
radical
effect
(PRE).
In
this
Review,
an
explanation
PRE
supported
by
simulations
simple
model
systems
provided.
Radical
stabilities
discussed
within
context
their
lifetimes,
various
examples
PRE‐mediated
radical–radical
in
synthesis
summarized.
It
shown
that
restricted
to
coupling
with
transient
radical.
If
one
partner
longer‐lived
than
other
radical,
operates
achieved.
important
point
expands
scope
chemistry.
The
Review
divided
into
parts,
namely
1)
or
organic
2)
“radical–metal
crossover
reactions”;
here,
metal‐centered
species
more
generally
transition‐metal
complexes
able
react
discussed—a
field
has
flourished
recently.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(19), P. 6152 - 6163
Published: Oct. 6, 2018
The
union
of
photoredox
and
nickel
catalysis
has
resulted
in
a
renaissance
radical
chemistry
as
well
the
use
nickel-catalyzed
transformations,
specifically
for
carbon-carbon
bond
formation.
Collectively,
these
advances
address
longstanding
challenge
late-stage
cross-coupling
functionalized
alkyl
fragments.
Empowered
by
notion
that
photocatalytically
generated
radicals
readily
undergo
capture
Ni
complexes,
wholly
new
feedstocks
have
been
realized.
Herein,
we
highlight
recent
developments
several
types
cross-couplings
are
accessible
exclusively
through
this
approach.
Organic Process Research & Development,
Journal Year:
2019,
Volume and Issue:
23(6), P. 1213 - 1242
Published: May 7, 2019
High-throughput
experimentation
(HTE)
has
revolutionized
the
pharmaceutical
industry,
most
notably
allowing
for
rapid
screening
of
compound
libraries
against
therapeutic
targets.
The
past
decade
also
witnessed
extension
HTE
principles
toward
realm
small-molecule
process
chemistry.
Today,
major
companies
have
created
dedicated
groups
within
their
development
teams,
invested
in
automation
technology
to
accelerate
screening,
or
both.
industry's
commitment
accelerating
led
innovations
space.
This
review
will
deliver
an
overview
latest
best
practices
currently
taking
place
our
teams
chemistry
by
sharing
frequently
studied
transformations,
perspective
next
several
years
field,
and
manual
automated
tools
enable
experimentation.
A
series
case
studies
are
presented
exemplify
state-of-the-art
workflows
developed
laboratories.
